Production of light olefins

ABSTRACT

The process for the production of light olefins from a feedstock comprising at least an aliphatic hetero compound comprising contacting said feedstock in the presence of an aromatic diluent with a non-zeolitic molecular sieve at effective process conditions to produce light olefins.

FIELD OF THE INVENTION

The present invention relates to a new catalytic process for theproduction of light olefins, i.e., olefins having not more than fourcarbon atoms, from a feedstock comprising aliphatic hetero compounds ormixtures thereof in the presence of a non-zeolitic molecular sievecatalyst.

BACKGROUND OF THE INVENTION

As a result of the limited availability and high cost of petroleumsources the cost of producing chemicals from such petroleum sources hasbeen steadily increasing. Further, many in the chemical industry, aswell as elsewhere, have raised the dire prediction of significant oilshortages in the not too distant future. As a result, the search for analternative, low cost and more readily available raw material forchemical synthesis has been intense with the ultimate goal being thederivation of valuable chemical products from non-petroleum sources.

Such readily available sources are methanol, ethanol and theirderivatives which may be manufactured from non-petroleum sources such asby fermentation or from synthesis gas, i.e., a mixture of oxides ofcarbon and hydrogen. Synthesis gas may be derived by the combustion ofany carbonaceous material including coal, or any organic material, suchas hydrocarbons, carbohydrates and the like. Thus, the use of methanoland its derivatives to form chemical products is particularly desirablein providing such a non-petroleum based route. The manufacture ofmethanol from synthesis gas by a heterogeneous catalytic reaction ispresently an efficient commercial process.

Although methanol and its derivatives have for some time been consideredas desirable starting materials for the manufacture of chemicals (whichit is, e.g., in the manufacture of formaldehyde), the use of such as areplacement for petroleum or natural gas in commercial chemicalsyntheses has not been vast. If processes can be developed for the useof methanol and its derivatives for the commercial manufacture in largevolume of chemical products or intermediates then the present dependenceon petroleum sources as the basic raw material for chemical synthesismay be substantially lessened.

One proposed way to use methanol and its derivatives to manufacturechemical products is by catalytically converting them with crystallinealuminosilicate zeolites. Representative of the various contemplatedprocesses using such crystalline aluminosilicate zeolites, and as morecompletely discussed hereinafter, are those processes disclosed in U.S.Pat. Nos.: 3,894,107; 4,046,825; 4,062,905; 4,079,095; 4,079,096;3,911,041; and 4,049,573. What appears to be evident from the abovepatents, as well as other patents, is that the process is tied to theparticular catalyst employed yielding differences in: product ratios (aswell as by-product formation); catalyst life; conversion to product;selectivity to product; catalyst attrition; and the effects fromadditives to the catalytic process. The significance of thesedifferences is readily apparent by reviewing the divergent results ofthe published art wherein various catalysts have been employed for theconversion of methanol to light olefin products. Representative of thisart are: European Application No. 6,501 (catalyst is HZSM-5); Europeanapplication No. 2,492 (catalyst is Mn exchanged 13X zeolite); GermanOffen. No. 2,909,928 (catalyst is Fe exchanged Silicalite); Agnew. Chem.Int. Ed., 19, 2 (1980), 126-7 (catalyst is Mn exchanged Chabazite anderionite); South African No. 78/2527 (catalyst is CaH-Fu-1 zeolite); andEuropean Application No. 11,900 (catalyst is boron modified silica).

For example, German Offen. No. 2,909,928 discloses a 95-100 percentconversion with 5.2 weight percent of the product as ethylene, whereasthe publication Agnew. Chem. Int. Ed., 19, 2 (1980), 126-7 discloses aconversion of about 82 percent with 35.7 weight percent of the productas ethylene.

A brief discussion of selected patents and publications will furtherserve to point out differences involved in the conversion of methanoland derivatives thereof to light olefin products.

U.S. Pat. No. 4,062,905 discloses a process for the conversion ofmethanol, dimethyl ether or mixtures thereof to hydrocarbon productsrich in ethylene and propylene using a catalyst comprising a crystallinealuminosilicate zeolite characterized by pores, the major dimension ofwhich, are less than 6 Angstroms, the pores being further characterizedby pore windows of about a size as would be provided by 8-membered ringsof oxygen atoms. The process is alleged to have the capability undercertain conditions of producing less than 20 weight percent methane byweight of the hydrocarbon product. The claimed correlation in the patentbetween pore size, process conditions and the level of methaneproduction is admittedly specifically limited to the crystallinealuminosilicate zeolites, see the quote below.

The passage beginning at column 3, line 5 (also see Example 17) of U.S.Pat. No. 4,062,905 demonstrates this view:

"In addition to having the hereinabove described pore sizecharacteristics, the crystalline aluminosilicate zeolite utilized ascatalyst in the present process should have the capability of producinga hydrocarbon product containing less than 20 percent and preferably notmore than 10 percent by weight of methane. Thus, the calcium form ofzeolite A, having pores of approximately 5 Angstroms and commonlyreferred to as zeolite 5A, while satisfying the pore size requirementsfor zeolites useful as catalysts in the process described herein, isnevertheless, not a particularly feasible catalyst since under theconversion conditions utilized in such process, this zeolite producesconsiderable amounts of methane, i.e., far in excess of the specifiedmaximum of 20 weight percent characterizing the crystallinealuminosilicate zeolites which have been found to be effective inselectively converting methanol and/or dimethyl ether to ethylene andpropylene."

Even when a crystalline aluminosilicate zeolite having the desiredphysical and chemical properties is employed it may not be useful as acatalyst according to the patent's process. Thus, this patent disclosesthat the chemical composition of an aluminosilicate which has adesirable pore size may or may not be determinative as to whether itwill produce methane at a given rate such that less than 20 percent byweight methane is produced.

The specificity of the catalysts in this field is demonstrated by U.S.Pat. Nos. 4,079,096 and 4,079,095 which disclose processes for theconversion of methanol, dimethyl ether or mixtures thereof tohydrocarbon products, such as ethylene and propylene, by contacting themwith a catalyst comprising, respectively, a crystalline aluminosilicatezeolite of the erionite-offretite family and, the particularerionite-offretite of the crystalline aluminosilicate zeolite ZSM-34.The processes are limited to the use of crystalline aluminosilicateshaving substantially the same diffraction pattern as theerionite-offretite family.

U.S. Pat. No. 3,911,041 describes the conversion of methanol or dimethylether by contacting them with a crystalline aluminosilicate zeolitehaving a silica to alumina ratio of at least about 12, a constraintindex of about 1 to 12, and containing phosphorous deposited on thecrystal structure thereof in an amount of at least about 0.78 percent byweight. The phosphorous is disclosed as not in the framework of thecrystalline aluminosilicate, as can be determined from the preparationprocedure beginning at column 7, line 56 of the patent. The procedureset forth in the patent details that the crystalline aluminosilicatezeolite is formed prior to the addition of the phosphorus-containingcompound, after which the phosphorous-containing compound is "reacted"with the surface sites of the zeolite to provide a surface treatedmaterial. Further, X-ray diffraction analyses of the zeolite before andafter treatment with a phosphorus-containing compound showedsubstantially identical interplanar spacings (see Column 8, lines 54 to64) indicating that no phosphorus was present in the framework. Thesurface treatment of the crystalline aluminosilicates is predicated onthe patentees' belief that the number and strength of thealuminosilicates acid sites is related to the activity.

U.S. Pat. No. 4,049,573 describes a crystalline aluminosilicate zeolitehaving a silica to alumina ratio of at least 12 and a constraint indexwithin the approximate range of 1 to 12, and having deposited thereon(as one of several possibilities) between about 0.25 and about 10percent by weight of phosphorus oxide in combination with between about0.25 and about 5 percent by weight of boron oxide and between about 2and about 15 percent by weight of magnesium oxide. As was the case inthe above-discussed U.S. Pat. No. 3,911,041, the phosphorous oxide,boron oxide and magnesium oxide are not incorporated into the zeoliteframework but, instead, are added to the zeolite after the framework ofthe aluminosilicate zeolite has been formed, i.e., are provided as apost treatment of the aluminosilicate zeolite, apparently for the samereason.

As is evident from the above, the interest in selective catalysts forthe manufacture of light olefins from methanol has been achieved from aspecial aluminosilicate structure or by achieving modifications ofaluminosilicates by deposition with special additives. As above-noted,one of these was to deposit a phosphorous-containing compound (termed"doping" herein) in combination with a number of other compounds on analuminosilicate zeolite.

U.S. Pat. Nos. 3,911,041 and 4,049,573, reports the sorption ofphosphate ions onto amorphous metal oxides and combinations of metaloxides. Such sorptions of phosphate ions has been intensively studied insuch areas as in the chemistry of soil, although such studies have notheretofore reported a crystalline microporous phosphate-containingmaterial. For example, see: S. S. S. Rajan and K. W. Perrott, J. SoilSci., 26, 257 (1975); J. A. Veith and G. Sposito, Soil. Sci., Soc. Am.J., 41, 870 (1977); E. A. Ferreiro and S. G. DeBussetto, Agrochimica,24,184 (1980).

It has been reported (D. McConnell, Ameri. Min., 37, 609 (1952)) thatcertain natural aluminosilicate zeolites may have PO₂ ⁺ substitutioninto the tetrahedral framework with such a substitution being reportedin viseite which is considered to be isostructural with analcime. D.McConnell reported an elemental composition of:

    5 CaO:5Al.sub.2 O.sub.3 :3SiO.sub.2 :3P.sub.2 O.sub.5 :n H.sub.2 O.

This report should be viewed cautiously, if not with skepticism, in viewof the considerable question of agreement on the X-ray powderdiffraction patterns of such a substituted viseite and analcime owing tothe highly defective structure (with dangling --OH groups wherevertetrahedral cation vacancies occur) resorted to in order to substantiatesuch structures as being isostructural.

R. M. Barrer and D. J. Marshall (J. Chem. Soc., 1965, 6616 and 6621)reported the attempted substitution of phosphorus in aluminosilicatesduring hydrothermal crystallizations in the system, in respect to thefollowing:

    Al.sub.2 O.sub.3 --SiO.sub.2 --P.sub.2 O.sub.5 --base--H.sub.2 O

Although phosphate was observed to co-precipitate with thealuminosilicates in this system there was no evidence that analuminosilicophosphate framework had formed.

R. M. Barre and M. Liguornick (J. Chem. Soc., Dalton Trans., 2126(1974)) reported that by use of metakaolinite and phosphoric acid, andin some instances by further addition of silica, that zeolites wereformed having an extremely low content of phosphorous with a maximum of0.0117 atoms of phosphorus present per atom of aluminum. The authorsexplanation for this very low phosphorous content is that phosphateanions were trapped in cavities within the zeolite framework rather thanactually being in the framework.

U.S Pat. No. 3,443,892 discloses a process for making Zeolite X bymixing aluminum phosphate with hot sodium silicate to give anas-synthesized product having the general formula:

    (0.5-1.1)Na.sub.2 O.sub.3 :Al.sub.2 O.sub.3 :(0-0.2)P.sub.2 O.sub.5 : (2.3-3.3)SiO.sub.2 :(0-7.2)H.sub.2 O

No chemical data is disclosed by the patentee for determining theframework structure and the patent reguires that the ratio of SiO₂ toNa₂ O in the reaction mixture must be less than 1.

The synthesis of aluminosilicophosphate zeolite analogues havingphosphorus incorporated into the tetrahedral sites of the zeolite-typeframework during hydrothermal synthesis employing substantial amounts ofalkali metal cations has been reported by E. M. Flanigen and R. W. Groseat Advances in Chem., Series No. 101 pages 76-101 (1971). (Also see:Canadian Patent No. 911,410, issued Oct. 3, 1972 to Robert W. Grose andEdith M. Flanigen) In this report the authors reported compositions withthe following types of zeolite-type frameworks: analcime, chabazite,phillipsite-harmotome, Type A zeolite, Type L zeolite, and Type B (P)zeolite. These compositions were reported to contain between 5 and 25percent by weight P₂ O₅ incorporated into the zeolite-type frameworks.The substitution of phosphorus for silicon did not appear to impartbeneficial properties to the compositions not possessed by analogousaluminosilicate compositions, although differences were reported in someof the compositions, e.g., reduced adsorption capacity and reducedthermal stability on thermal activation. Many of the physical andchemical properties of the phosphorus-substituted analogues wereinferior to those of the unsubstituted species.

U.S. Pat. No. 4,440,871 discloses a novel family ofsilicoaluminophosphates (SAPOs) and U.S. Pat. No. 4,449,327 discloses aprocess employing the SAPOs of U.S. Pat. No. 4,440,871 for theconversion of methanol, dimethyl ether, etc., to light olefins.

DISCLOSURE OF THE INVENTION

This invention comprises a process for the catalytic conversion of afeedstock comprising one or more aliphatic hetero compounds comprisingalcohols, halides, mercaptans, sulfides, amines, ethers and carbonylcompounds or mixtures thereof to a hydrocarbon product containing lightolefinic products, i.e., C₂, C₃ and/or C₄ olefins. The feedstock iscontacted with a non-zeolitic molecular sieve (as hereinafter defined)at effective process conditions to produce light olefins. The process ispreferably carried out in the presence of a diluent that is correlatedto the selected non-zeolitic molecular sieve such that the averagekinetic diameter of the diluent is greater than the median pore size ofthe non-zeolitic molecular sieve.

It has been found that non-zeolitic molecular sieves (denominated"NZMSs") are efficient catalysts for the conversion of a feedstockcomprising aliphatic hetero compounds, preferably methanol, ethanol,dimethyl ether, diethyl ether or mixtures thereof, to light olefins andthat the two carbon, three carbon, and four carbon (C₂ -C₄) light olefinproduct content of the hydrocarbon reaction products generally comprisesa major portion of the hydrocarbon products while methane and aromatics(other than the diluent) typically comprise a minor portion thereof.

DESCRIPTION OF THE INVENTION

The instant process relates to making light olefins containing 2 to 4carbon atoms wherein said process comprises contacting a feedstock witha non-zeolitic molecular sieve as described hereinafter:

NON-ZEOLITIC MOLECULAR SIEVES ("NZMS")

The term "non-zeolitic molecular sieves" or "NZMS" is defined in theinstant invention to include "ELAPSO" molecular sieves as disclosed inU.S. Ser. No. 600,312, filed Apr. 13, 1984 and certain "MeAPO", "FeAPO","TAPO" and "ELAPO" molecular sieves, as hereinafter described.Crystalline metal aluminophosphates (MeAPOs where "Me" is at least oneof Mg, Mn, Co and Zn) are disclosed in U.S. Pat. No. 4,567,029, issuedJan. 28, 1986; crystalline ferroaluminophosphates (FeAPOs) are disclosedin U.S. Pat. No. 4,554,143, issued Nov. 19, 1985; titaniumaluminophosphates (TAPOs) are disclosed in U.S. Pat. No. 4,500,651,issued Feb. 19, 1985; certain non-zeolitic molecular sieves ("ELAPO")are disclosed in EPC Application No. 85104386.9 (Publication No.0158976, published Oct. 13, 1985 and 85104388.5 (Publication No. 158349,published Oct. 16, 1985); and ELAPSO molecular sieves are disclosed incopending U.S. Ser. No. 600,312, filed Apr. 13, 1984 (EPC PublicationNo. 0159624, published Oct. 30, 1985). The aforementioned applicationsand patents are incorporated herein by reference thereto. Thenomenclature employed herein to refer to the members of theaforementioned NZMSs is consistent with that employed in theaforementioned applications or patents. A particular member of a classis generally referred to as a "-n" species wherein "n" is an integer,e.g., MeAPO-11, MeAPO-31 and ELAPSO-31. In the following discussion onNZMSs set forth hereinafter the mole fraction of the NZMSs are definedas compositional values which are plotted in phase diagrams in each ofthe identified patents, published applications or copendingapplications.

ELAPSO MOLECULAR SIEVES

"ELAPSO" molecular sieves are described in copending U.S. Ser. No.600,312, filed Apr. 13, 1984, (EPC Publication No. 0159,624, publishedOct. 30, 1985, incorporated herein by reference) as crystallinemolecular sieves having three-dimensional microporous frameworkstructures of ELO₂, AlO₂, PO₂, SiO₂ oxide units and having an empiricalchemical composition on an anhydrous basis expressed by the formula:

    mR:(El.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the molar amount of "R"present per mole of (EL_(w) Al_(x) P_(y) Si_(z))O₂ and has a value offrom zero to about 0.3; "EL" represents at least one element capable offorming a three dimensional oxide framework, "EL" is characterized as anelement having a mean "T-O" distance in tetrahedral oxide structuresbetween about 1.51 Angstroms and about 2.06 Angstroms, "EL" has a cationelectronegativity between about 125 kcal/g-atom to about 310 kcal/m-atomand "EL" is capable of forming stable M--O--P, M--O--Al or M--O--M bondsin crystalline three dimensional oxide structures having a "M--O" bonddissociation energy greater than about 59 kcal/g-atom at 298° K.; and"w", "x", "y" and "z" represent the mole fractions of "EL", aluminum,phosphorus and silicon, respectively, present as framework oxides saidmole fractions being within the limiting compositional values or pointsas follows:

    ______________________________________                                        Mole Fraction                                                                 Point  x            y            (z + w)                                      ______________________________________                                        A      0.60         0.39 - (0.01)p                                                                             0.01 (p + 1)                                 B      0.39 - (0.01 p)                                                                            0.60         0.01 (p + 1)                                 C      0.01         0.60         0.39                                         D      0.01         0.01         0.98                                         E      0.60         0.01         0.39                                         ______________________________________                                    

where "p" is an integer corresponding to the number of elements "El" inthe (El_(w) Al_(x) P_(y) Si_(z))O₂ constituent.

The "ELAPSO" molecular sieves are also described as crystallinemolecular sieves having three-dimensional microporous frameworkstructures of ELO₂, AlO₂, SiO₂ and PO₂ tetrahedral oxide units andhaving an empirical chemical composition on an anhydrous basis expressedby the formula:

    mR:(El.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the molar amount of "R"present per mole of (El_(w) Al_(x) P_(y) Si_(z))O₂ and has a value offrom zero to about 0.3; "EL" represents at least one element capable offorming a framework tetrahedral oxide and is selected from the groupconsisting of arsenic, beryllium, boron, chromium, cobalt, gallium,germanium, iron, lithium, magnesium, manganese, titanium and zinc; and"w", "x", "y" and "z" represent the mole fractions of "EL", aluminum,phosphorus and silicon, respectively, present as tetrahedral oxides saidmole fractions being within the limiting compositional values or pointsas follows:

    ______________________________________                                        Mole Fraction                                                                 Point  x            y            (z + w)                                      ______________________________________                                        a      0.60         0.39 - (0.01)p                                                                             0.01 (p + 1)                                 b      0.39 - (0.01 p)                                                                            0.60         0.01 (p + 1)                                 c      0.10         0.55         0.35                                         d      0.55         0.10         0.35                                         ______________________________________                                    

where "p" is as above defined.

The "ELAPSO" molecular sieves include numerous species which areintended herein to be within the scope of the term "non-zeoliticmolecular sieves" such being disclosed in the following copending andcommonly assigned applications, incorporated herein by referencethereto:

    ______________________________________                                        U.S. Ser. No.                                                                             Filed         NZMS                                                ______________________________________                                        600,174     April 13, 1984                                                                              CoAPSO                                              600,173     April 13, 1984                                                                              FeAPSO                                                                        (now U.S. Pat. No.                                                            4,683,217, issued                                                             July 28, 1987)                                      600,180     April 13, 1984                                                                              MgAPSO                                              600,175     April 13, 1984                                                                              MnAPSO                                                                        (now U.S. Pat. No.                                                            4,686,092, issued                                                             August 11, 1987)                                    600,179     April 13, 1984                                                                              TiAPSO                                                                        (now U.S. Pat. No.                                                            4,684,617, issued                                                             August 4, 1987)                                     600,170     April 13, 1984                                                                              ZnAPSO                                              600,168     April 13, 1984                                                                              CoMgAPSO                                            600,182     April 13, 1984                                                                              CoMnMgAPSO                                          845,984     March 31, 1986                                                                              AsAPSO                                              845,255     March 28, 1986                                                                              BAPSO                                               841,752     March 20, 1986                                                                              BeAPSO                                              852,174     April 15, 1986                                                                              CAPSO                                               845,985     March 31, 1986                                                                              GaAPSO                                              852,175     April 15, 1986                                                                              GeAPSO                                              847,227     April 12, 1986                                                                              LiAPSO                                              ______________________________________                                    

TiAPSO MOLECULAR SIEVES

The TiAPSO molecular sieves of U.S. Ser. No. 600,179, filed Apr. 13,1984 have three-dimensional microporous framework structures of TiO₂,AlO₂, PO₂ and SiO₂ tetrahedral oxide units having an empirical chemicalcomposition on an anhydrous basis expressed by the formula:

    mR:(Ti.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the molar amount of "R"present per mole of (Ti_(w) Al_(x) P_(y) Si_(z))O₂ and has a value offrom zero to about 0.3; and "w", "x", "y" and "z" represent the molefractions of titanium, aluminum, phosphorus and silicon, respectively,present as tetrahedral oxides and each has a value of at least 0.01. Themole fractions "w", "x", "y" and "z" are generally defined being withinthe limiting compositional values or points as follows:

    ______________________________________                                        Mole Fraction                                                                 Point   x             y      (z + w)                                          ______________________________________                                        A       0.60          0.38   0.02                                             B       0.38          0.60   0.02                                             C       0.01          0.60   0.39                                             D       0.01          0.01   0.98                                             E       0.60          0.01   0.39                                             ______________________________________                                    

In a subclass of TiAPSO molecular sieves the values "w", "x", "y" and"z" in the above formula are within the tetragonal compositional areadefined by points a, b, c and d, said points a, b, c and d representingthe following values for "w", "x", "y" and "z":

    ______________________________________                                        Mole Fraction                                                                 Point   x             y      (z + w)                                          ______________________________________                                        a       0.55          0.43   0.02                                             b       0.43          0.55   0.02                                             c       0.10          0.55   0.35                                             d       0.55          0.10   0.35                                             ______________________________________                                    

TiAPSO compositions are generally synthesized by hydrothermalcrystallization from a reaction mixture containing active resources oftitanium, silicon, aluminum and phosphorus, and preferably an organictemplating, i.e., structure-directing, agent, preferably a compound ofan element or Group VA of the Periodic Table, and/or optionally analkali or other metal. The reaction mixture is generally placed in asealed pressure vessel, preferably lined with an inert plastic materialsuch as polytetrafluoroethylene and heated, preferably under autogenouspressure at a temperature between 50° C. and 250° C., and preferablybetween 100° C. and 200° C. until crystals of the TiAPSO product areobtained, usually a period of from hours to several weeks. Generally,the crystallization time is from about 2 hours to about 30 days andtypically from about 4 hours to about 20 days. The product is recoveredby any convenient method such as centrifugation or filtration.

In synthesizing the TiAPSO, it is preferred to employ a reaction mixturecomposition expressed in terms of the molar ratios as follows:

    aR:(Ti.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 :bH.sub.2 O

wherein "R" is an organic templating agent; "a" is the amount of organictemplating agent "R" and has a value of from zero to about 6 and ispreferably an effective amount within the range of greater than zero (0)to about 6; "b" has a value of from zero (0) to about 500, preferablybetween about 2 and about 300; and "w", "x", "y" and "z" represent themole fractions of titanium, aluminum, phosphorus and silicon,respectively, and each has a value of at least 0.01.

In one embodiment the reaction mixture is selected such that the molefractions "w", "x", "y" and "z" are generally defined as being withinthe limiting compositional values or points as follows:

    ______________________________________                                        Mole Fraction                                                                 Point   x             y      (z + w)                                          ______________________________________                                        F       0.60          0.38   0.02                                             G       0.38          0.60   0.02                                             H       0.01          0.60   0.39                                             I       0.01          0.01   0.98                                             J       0.60          0.01   0.39                                             ______________________________________                                    

In the foregoing expression of the reaction composition, the reactantsare normalized with respect to the total of "w", "x", "y" and "z" suchthat (w+x+y+z)=1.00 mole. Molecular sieves containing titanium,aluminum, phosphorus and silicon as framework tetrahedral oxides areprepared as follows:

Preparative Reagents

TiAPSO compositions are typically prepared using numerous regents.Typical reagents which may be employed and abbreviations employed inU.S. Ser. No. 600,179 for such reagents are as follows:

(a) Alipro: aluminum isopropoxide;

(b) LUDOX-LS: LUDOX-LS is the tradename of DuPont for an agueoussolution of 30 weight percent SiO₂ and 0.1 weight percent Na₂ O;

(c) H₃ PO₄ : 85 weight percent aqueous phosphoric acid;

(d) Tiipro: titanium isopropoxide;

(e) TEAOH: 40 weight percent aqueous solution of tetraethylammoniumhydroxide;

(f) Pr₂ NH: di-n-propylamine, (C₃ H₇)₂ NH;

(g) Pr₃ NH: tri-n-propylamine, (C₃ H₇)₃ N;

(h) Quin: Quinuclidine, (C₇ H₁₃ N);

(i) MQuin: Methyl Quinuclidine hydroxide, (C₇ H₁₃ NCH₃ OH); and

(j) C-hex: cyclohexylamine.

Preparative Procedures

TiAPSOs may be prepared by forming a starting reaction mixture by addingthe H₃ PO₄ and the water. This mixture is mixed and to this mixturealuminum isopropoxide is added. This mixture is then blended until ahomogeneous mixture is observed. To this mixture the LUDOX-LS is addedand the resulting mixture blended (about 2 minutes) until a homogeneousmixture is observed.

The titanium isopropoxide is added to the above mixture and theresulting mixture blended until a homogeneous mixture is observed. Theorganic templating agent is then added to the resulting mixture and theresulting mixture blended until a homogeneous mixture is observed, i.e.,about 2 to 4 minutes. When the organic templating agent is quinuclidinethe procedure is modified such that the quinuclidine is dissolved inabout one half the water and accordingly the H₃ PO₄ is mixed with aboutone half the water. (The pH of the mixture is measured and adjusted fortemperature). The mixture is then placed in a lined(polytetrafluoroethylene) stainless steel pressure vessel and digestedat a temperature (150° C. or 200° C.) for a time or placed in linedscrew top bottles for digestion at 100° C. Digestions are typicallycarried out at the autogenous pressure.

The products are removed from the reaction vessel and cooled.

MgAPSO MOLECULAR SIEVES

The MgAPSO molecular sieves of U.S. Ser. No 600,180, filed Apr. 13, 1984(EPC Publication No. 0 158 348, published Oct. 16, 1985), havethree-dimensional microporous framework structures of MgO₂ ⁻², AlO₂ ⁻,PO₂ ⁺ and SiO₂ tetrahedral oxide units and have an empirical chemicalcomposition on an anhydrous basis expressed by the formula:

    mR:(Mg.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the molar amount of "R"present per mole of (Mg_(w) Al_(x) P_(y) Si_(z))O₂ and has a value fromzero (0) to about 0.3; and "w", "x", "y" and "z" represent the molefractions of magnesium, aluminum, phosphorus and silicon, respectively,present as tetrahedral oxides and each preferably has a value of atleast 0.01. The mole fractions "w", "x", "y" and "z" are generallydefined as being within the limiting compositional values or points asfollows:

    ______________________________________                                        Mole Fraction                                                                 Point   x             y      (z + w)                                          ______________________________________                                        A       0.60          0.38   0.02                                             B       0.39          0.59   0.02                                             C       0.01          0.60   0.39                                             D       0.01          0.01   0.98                                             E       0.60          0.01   0.39                                             ______________________________________                                    

In a preferred subclass of the MgAPSO molecular sieves the values "w","x", "y" and "z" in the above formula are within the limitingcompositional values or points as follows:

    ______________________________________                                        Mole Fraction                                                                 Point   x             y      (z + w)                                          ______________________________________                                        a       0.55          0.43   0.02                                             b       0.43          0.55   0.02                                             c       0.10          0.55   0.35                                             d       0.55          0.10   0.35                                             ______________________________________                                    

MgAPSO compositions are generally synthesized by hydrothermalcrystallization for an effective time at effective pressures andtemperatures from a reaction mixture containing reactive sources ofmagnesium, silicon, aluminum and phosphorus, an organic templating,i.e., structure-directing, agent, preferably a compound of an element ofGroup VA of the Periodic Table, and may be an alkali or other metal. Thereaction mixture is generally placed in a sealed pressure vessel,preferably lined with an inert plastic material such aspolytetrafluoroethylene and heated, preferably under autogenous pressureat a temperature between 50° C. and 250° C., and preferably between 100°C. and 200° C. until crystals of the MgAPSO product are obtained,usually a period of from several hours to several weeks. Generally, thecrystallization period will be from about 2 hours to about 30 days withit typically being from about 4 hours to about 20 days for obtainingMgAPSO crystals. The product is recovered by any convenient method suchas centrifugation or filtration.

In synthesizing the MgAPSO compositions, it is preferred to employreaction mixture compositions expressed in terms of the molar ratios asfollows:

    aR:(Mg.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 :bH.sub.2 O

wherein "R" is an organic templating agent; "a" is the amount of organictemplating agent "R" and can have a value within the range of from zero(0) to about 6 and is more preferably an effective amount greater thanzero to about 6; "b" has a value of from zero (0) to about 500,preferably between about 2 and about 300; and "w", "x", "y" and "z"represent the mole fractions of magnesium, aluminum, phosphorus andsilicon, respectively, and each has a value of at least 0.01.

In one embodiment the reaction mixture is selected such that the molefractions "w", "x", "y" and "z" are generally defined as being withinthe limiting compositional values or points as follows:

    ______________________________________                                        Mole Fraction                                                                 Point   x             y      (z + w)                                          ______________________________________                                        F       0.60          0.38   0.02                                             G       0.38          0.60   0.02                                             H       0.01          0.60   0.39                                             I       0.01          0.01   0.98                                             J       0.60          0.01   0.39                                             ______________________________________                                    

In the foregoing expression of the reaction composition, the reactantsare normalized with respect to the total of "w", "x", "y" and "z" suchthat (w+x+y+z)=1.00 mole. Molecular sieves containing magnesium,aluminum, phosphorus and silicon as framework tetrahedral oxides areprepared as follows:

Preparative Reagents

MgAPSO compositions are prepared using numerous reagents. Typicalreagents which may be employed to prepare MgAPSOs include:

(a) Alipro: aluminum isopropoxide;

(b) CATAPAL: Trademark of Condea for hydrated pseudoboehmite;

(c) LUDOX-LS: Trademark of DuPont for an aqueous solution of 30 weightpercent SiO₂ and 0.1 weight percent Na₂ O;

(d) Mg(Ac)₂ : magnesium acetate tetrahydrate, Mg(C₂ H₃ O₂).4H₂ O;

(e) H₃ PO₄ : 85 weight percent aqueous phosphoric acid in water;

(f) TBAOH: tetraethylammonium hydroxide (40 wt. % in water);

(g) Pr₂ NH: di-n-propylamine;

(h) Pr₃ NH: tri-n-propylamine;

(i) Quin: Quinuclidine;

(j) MQuin: Methyl Quinuclidine hydroxide, (17.9% in water);

(k) C-hex: cyclohexylamine;

(l) TEAOH: tetraethylammonium hydroxide (40 wt. % in water);

(m) DEEA: Diethylethanolamine;

(n) i-Pr₂ NH: di-isopropylamine;

(o) TEABr: tetraethylammonium bromide; and

(p) TPAOH: tetrapropylammonium hydroxide (40 wt. % in water).

Preparative Procedures

The MgAPSO compositions may be prepared by preparing reaction mixtureshaving a molar composition expressed as:

    eR:fMgO:hAl.sub.2 O.sub.3 :iP.sub.2 O.sub.5 :gSiO.sub.2 :jH.sub.2 O

wherein e, f, g, h, i and j represent the moles of template R, magnesium(expressed as the oxide), SiO₂, Al₂ O₃, P₂ O₅ (H₃ PO₄ expressed as P₂O₅) and H₂ O, respectively.

The reaction mixtures may be prepared by the following representativeprocedures, designated hereinafter as Methods A, B and C.

Method A

The reaction mixture is prepared by mixing the ground aluminum source(Alipro or CATAPAL) with the H₃ PO₄ and water on a gradual basis withoccasional cooling with an ice bath. The resulting mixture is blendeduntil a homogeneous mixture is observed. When the aluminum source isCATAPAL the water and H₃ PO₄ is first mixed with the CATAPAL addedthereto. The magnesium acetate is dissolved in portion of the water andis then added followed by addition of the LUDOX-LS. The combined mixtureis blended until a homogenous mixture is observed. The organictemplating agent is added to this mixture and blended until a homogenousmixture is observed. The resulting mixture (final reaction mixture) isplaced in a lined (polytetrafluoroethylene) stainless steel pressurevessel and digested at a temperature (150° C. or 200° C.) for aneffective time. Alternatively, if the digestion temperature is 100° C.the final reaction mixture is placed in a lined(polytetrafluoroethylene) screw top bottle for a time. Digestions aretypically carried out at the autogenous pressure. The products areremoved from the reaction vessel, cooled and evaluated as set forthhereinafter.

Method B

When method B is employed the organic templating agent isdi-n-propylamine. The aluminum source, silicon source and one-half ofthe water are first mixed and blended until a homogeneous mixture isobserved. A second solution was prepared by mixing the remaining water,the H₃ PO₄ and the magnesium acetate. This solution is then added to theabove mixture. The magnesium acetate and H₃ PO₄ solution is then addedto the above mixture and blended until a homogeneous mixture isobserved. The organic templating agent(s) is then added and theresulting reaction mixture digested and product recovered as is done inMethod A.

Method C

Method C is carried out by mixing aluminum isopropoxide, LUDOX LS andwater in a blender or by mixing water and aluminum isopropoxide in ablender followed by addition of the LUDOX LS. H₃ PO₄ and magnesiumacetate are then added to this mixture. The organic templating agent isthen added to the resulting mixture and digested and product recoveredas is done in Method A.

MnAPSO MOLECULAR SIEVES

The MnAPSO molecular sieves of U.S. Ser. No. 600,175, filed Apr. 13,1984 have a framework structrue of MnO₂ ⁻², AlO₂ ⁻, PO₂ ⁺, and SiO₂tetrahedral units having an empirical chemical composition on ananhydrous basis expressed by the formula:

    mR:(Mn.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the molar amount of "R"present per mole of (Mn_(w) Al_(x) P_(y) Si_(z))O₂ and has a value ofzero to about 0.3; and "w", "x", "y" and "z" represent the molefractions of element manganese, aluminum, phosphorus and silicon,respectively, present as tetrahedral oxides. The mole fractions "w","x", "y" and "z" are generally defined as being within the limitingcompositional values or points as follows:

    ______________________________________                                        Mole Fraction                                                                 Point   x             y      (z + w)                                          ______________________________________                                        A       0.60          0.38   0.02                                             B       0.38          0.60   0.02                                             C       0.01          0.60   0.39                                             D       0.01          0.01   0.98                                             E       0.60          0.01   0.39                                             ______________________________________                                    

The values of w, x, y and z may be as follows:

    ______________________________________                                        Mole Fraction                                                                 Point   x             y      (z + w)                                          ______________________________________                                        a       0.55          0.43   0.02                                             b       0.43          0.55   0.02                                             c       0.10          0.55   0.35                                             d       0.55          0.10   0.35                                             ______________________________________                                    

MnAPSO compositions are generally synthesized by hydrothermalcrystallization from a reaction mixture containing reactive sources ofmanganese, silicon, aluminum and phosphorus, preferably an organictemplating, i.e., structure-directing, agent, preferably a compound ofan element of Group VA of the Periodic Table, and/or optionally analkali or other metal. The reaction mixture is generally placed in asealed pressure vessel, preferably lined with an inert plastic materialsuch as polytetrafluoroethylene and heated, preferably under autogenouspressure at a temperature between about 50° C. and about 250° C., andpreferably between about 100° C. and about 200° C. until crystals of theMnAPSO product are obtained, usually a period of from several hours toseveral weeks. Typical effective times of from 2 hours to about 30 dayswith generally from about 4 hours to about 20 days have been observed.The product is recovered by any convenient method such as centrifugationor filtration.

In synthesizing the MnAPSO compositions, it is preferred to employ areaction mixture composition expressed in terms of the molar ratios asfollows:

    aR:(Mn.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 :bH.sub.2 O

wherein "R" is an organic templating agent; "a" is the amount of organictemplating agent "R" and has a value of from zero to about 6 and ispreferably an effective amount within the range of greater than zero (0)to about 6; "b" has a value of from zero (0) to about 500, preferablybetween about 2 and about 300; and "w", "x", "y" and "z" represent themole fractions of manganese, aluminum, phosphorus and silicon,respectively, and each has a value of at least 0.01.

In one embodiment the reaction mixture is selected such that the molefractions "w", "x", "y" and "z" are generally defined as being withinthe limiting compositional values or points as follows:

    ______________________________________                                        Mole Fraction                                                                 Point   x             y      (z + w)                                          ______________________________________                                        F       0.60          0.38   0.02                                             G       0.38          0.60   0.02                                             H       0.01          0.60   0.39                                             I       0.01          0.01   0.98                                             J       0.60          0.01   0.39                                             ______________________________________                                    

In the foregoing expression of the reaction composition, the reactantsare normalized with respect to the total of "w", "x", "y" and "z" suchthat (w+x+y+z)=1.00 mole. Molecular sieves containing manganese,aluminum, phosphorus and silicon as framework tetrahedral oxide unitsare prepared as follows:

Preparative Reagents

MnAPSO compositions may be prepared by using numerous reagents. Reagentswhich may be employed to prepare MnAPSOs include:

(a) Alipro: aluminum isopropoxide;

(b) CATAPAL: Trademark of Condea Corporation for hydratedpseudoboehmite;

(c) LUDOX-LS: LUDOX-LS is the tradename of DuPont for an aqueoussolution of 30 weight percent SiO₂ and 0.1 weight percent Na₂ O;

(d) H₃ PO₄ : 85 weight percent aqueous phosphoric acid;

(e) MnAc: Manganese acetate, Mn(C₂ H₃ O₂)₂.4H₂ O;

(f) TEAOH: 40 weight percent aqueous solution of tetraethylammoniumhydroxide;

TBAOH: 40 weight percent aqueous solution of tetrabutylammoniumhydroxide;

(h) Pr₂ NH: di-n-propylamine, (C₃ H₇)₂ NH;

(i) Pr₃ N: tri-n-propylamine (C₃ H₇)₃ N;

(j) Quin: Quinuclidine, (C₇ H₁₃ N);

(k) MQuin: Methyl Quinuclidine hydroxide, (C₇ H₁₃ NCH₃ OH);

(l) C-hex: cyclohexylamine;

(m) TMAOH: tetramethylammonium hydroxide;

(n) TPAOH: tetrapropylammonium hydroxide; and

(o) DEEA: 2-diethylaminoethanol.

Preparative Procedures

MnAPSOs are prepared by forming a starting reaction mixture by addingthe H₃ PO₄ to one half of the quantity of water. This mixture is mixedand to this mixture the aluminum isopropoxide or CATAPAL is added. Thismixture is then blended until a homogeneous mixture is observed. To thismixture the LUDOX LS is added and the resulting mixture blended (about 2minutes) until a homogeneous mixture is observed. A second mixture isprepared using the manganese acetate and the remainder (about 50%) ofthe water. The two mixtures are admixed and the resulting mixtureblended until a homogeneous mixture is observed. The organic templatingagent is then added to the resulting mixture and the resulting mixtureblended until a homogeneous mixture is observed, i.e., about 2 to 4minutes. (The pH of the mixture is measured and adjusted fortemperature). The mixture is then placed in a lined(polytetrafluoroethylene) stainless steel pressure vessel and digestedat a temperature (150° C. or 200° C.) for a time or placed in linedscrew top bottles for digestion at 100° C. Digestions are typicallycarried out at the autogenous pressure.

CoAPSO MOLECULAR SIEVES

The CoAPSO molecular sieves of U.S. Ser. No. 600,174, filed Apr. 13,1984 (EPC Publication No. 0 161 489, published Nov. 21, 1985), havethree-dimensional microporous framework structures of CoO₂ ⁻², AlO₂ ⁻,PO₂ ⁺ and SiO₂ tetrahedral units and have an empirical chemicalcomposition on an anhydrous basis expressed by the formula:

    mR:(Co.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the molar amount of "R"present per mole of (Co_(w) Al_(x) P_(y) Si_(z))O₂ and has a value offrom zero a 0.3; and "w", "x", "y" and "z" represent the mole fractionsof cobalt, aluminum, phosphorus and silicon, respectively, present astetrahedral oxides, where the mole fractions "w", "x", "y" and "z" areeach at least 0.01 and are generally defined, as being within thelimiting compositional values or points as follows:

    ______________________________________                                        Mole Fraction                                                                 Point   x             y      (z + w)                                          ______________________________________                                        A       0.60          0.38   0.02                                             B       0.38          0.60   0.02                                             C       0.01          0.60   0.39                                             D       0.01          0.01   0.98                                             E       0.60          0.01   0.39                                             ______________________________________                                    

In a preferred subclass of the CoAPSO molecular sieves the values of"w", "x", "y", and "z" in the above formula are within the limitingcompositional values or points as follows:

    ______________________________________                                        Mole Fraction                                                                 Point   x             y      (z + w)                                          ______________________________________                                        a       0.55          0.43   0.02                                             b       0.43          0.55   0.02                                             c       0.10          0.55   0.35                                             d       0.55          0.10   0.35                                             ______________________________________                                    

CoAPSO compositions are generally synthesized by hydrothermalcrystallization from a reaction mixture containing reactive sources ofcobalt, silicon, aluminum and phosphorus, an organic templating, i.e.,structure directing, agent, preferably a compound of an element of GroupVA of the Periodic Table, and optionally an alkali metal. The reactionmixture is generally placed in a sealed pressure vessel, preferablylined with an inert plastic material such as polytetrafluoroethylene andheated, preferably under autogenous pressure at an effective temperaturewhich is generally between 50° C. and 250° C. and preferably between100° C. and 200° C. until crystals of the CoAPSO product are obtained,usually for an effective time of from several hours to several weeks.Generally the effective crystallization time will be from about 2 hoursto about 30 days and typically from about 4 hours to about 20 days. Theproduct is recovered by any convenient method such as centrifugation orfiltration.

In synthesizing the CoAPSO, it is preferred to employ a reaction mixturecomposition expressed in terms of the molar ratios as follows:

    aR: (Co.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 : bH.sub.2 O

wherein "R" is an organic templating agent; "a" is the amount of organictemplating agent "R" and has a value of from zero to about 6 and ispreferably an effective amount within the range of greater than zero (0)to about 6; "b" has a value of from zero (0) to about 500, preferablybetween about 2 and 300; and "w", "x", "y" and "z" represent the molefractions of cobalt, aluminum, phosphorus and silicon, respectively, andeach has a value of at least 0.01. In a preferred embodiment thereaction mixture is selected such that the mole fractions "w", "x", "y"and "z" are generally defined as being within the limiting compositionalvalues or points as follows:

    ______________________________________                                        Mole Fraction                                                                 Point   x             y      (z + w)                                          ______________________________________                                        F       0.60          0.38   0.02                                             G       0.38          0.60   0.02                                             H       0.01          0.60   0.39                                             I       0.01          0.01   0.98                                             J       0.60          0.01   0.39                                             ______________________________________                                    

In the foregoing expression of the reaction composition, the reactantsare normalized with respect to the total of "w", "x", "y" and "z" suchthat (w+x+y+z)=1.00 mole. Molecular sieves containing cobalt, aluminum,phosphorus and silicon as framework tetrahedral oxide units are preparedas follows:

Preparative Reagents

CoAPSO compositions may be prepared using numerous reagents. Reagentswhich may be employed to prepared CoAPSOs include:

(a) Alipro: aluminum isoproproxide;

(b) CATAPAL: Trademark of Condea Corporation for pseudoboehmite;

(c) LUDOX-LS: Trademark of DuPont for an aqueous solution of 30 weightpercent SiO₂ and 0.1 weight percent Na₂ O;

(d) Co(Ac)₂ : cobalt acetate Co(C₂ H₃ O₂)₂ ·4H₂ O;

(e) CoSO₄ : cobalt sulfate (CoSO₄ ·7H₂ O);

(f) H₃ PO₄ : 85 weight percent phosphoric acid in water;

(g) TBAOH: tetrabutylammonium hydroxide (25 wt % in methanol);

(h) Pr₂ NH: di-n-propylamine, (C₃ H₇)₂ NH;

(i) Pr₃ N: tri-n-propylamine, (C₃ H₇)₃ N;

(j) Quin: Quinuclidine (C₇ H₁₃ N);

(k) MQuin: Methyl Quinuclidine hydroxide, (C₇ H₁₃ NCH₃ OH);

(l) C-hex: cyclohexylamine;

(m) TEAOH: tetraethylammonium hydroxide (40 wt. % in water);

(n) DEEA: diethanolamine;

(o) TPAOH: tetrapropylammonium hydroxide (40 wt. % in water); and

(p) TMAOH: tetramethylammonium hydroxide (40 wt. % in water).

Preparative Procedure

CoAPSO compositions may be prepared by preparing reaction mixtureshaving a molar composition expressed as:

    eR:fCoO:hAl.sub.2 O.sub.3 :iP.sub.2 O.sub.5 :gSiO.sub.2 :jH.sub.2 O

wherein e, f, h, i, g and j represent the moles of template R, cobalt(expressed as the oxide), Al,₂ O₃, P₂ O₅ (H₃ PO₄ expressed as P₂ O₅),SiO₂ and H₂ O, respectively.

The reaction mixtures are prepared by forming a starting reactionmixture comprising the H₃ PO₄ and one half of the water. This mixture isstirred and the aluminum source (Alipro or CATAPAL) added. The resultingmixture is blended until a homogeneous mixture is observed. The LUDOX-LSis then added to the resulting mixture and the new mixture blended untila homogeneous mixture is observed. The cobalt source (e.g., Co(Ac)₂,Co(SO₄) or mixtures thereof) is dissolved in the remaining water andcombined with the first mixture. The combined mixture is blended until ahomogeneous mixture is observed. The organic templating agent is addedto this mixture and blended for about two to four minutes until ahomogeneous mixture is observed. The resulting mixture (final reactionmixture) is placed in a lined (polytetrafluoroethylene) stainless steelpressure vessel and digested at a temperature (150° C., 200° C. or 225°C.) for a time. Digestions are typically carried out at the autogenouspressure. The products are removed from the reaction vessel and cooled.

ZnAPSO MOLECULAR SIEVES

The ZnAPSO molecular sieves of U.S. Ser. No. 600,170, filed Apr. 13,1984, (EPC Publication No. 0 158 975, published Oct. 23, 1985), compriseframework structures of ZnO₂ ⁻², AlO₂ ⁻, PO₂ ⁺ and SiO₂ tetrahedralunits having an anhydrous basis expressed chemical composition on ananhydrous basis expressed by the formula:

    mR: (Zn.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the molar amount of "R"present per mole of (Zn_(w) Al_(x) P_(y) Si_(z))O₂ and has a value ofzero to about 0.3; and "w", "x", "y" and "z" represent the molefractions of zinc, aluminum, phosphorus and silicon, respectively,present as tetrahedral oxides and each has a value of at least 0.01. Themole fractions "w", "x", "y" and "z" are generally defined being withinthe limiting compositional values or points as follows:

    ______________________________________                                        Mole Fraction                                                                 Point   x             y      (z + w)                                          ______________________________________                                        A       0.60          0.38   0.02                                             B       0.38          0.60   0.02                                             C       0.01          0.60   0.39                                             D       0.01          0.01   0.98                                             E       0.60          0.01   0.39                                             ______________________________________                                    

In a preferred subclass of ZnAPSO molecular sieves the values "w", "x","y" and "z" in the above formula are within the limiting compositionalvalues or points as follows:

    ______________________________________                                        Mole Fraction                                                                 Point   x             y      (z + w)                                          ______________________________________                                        a       0.55          0.43   0.02                                             b       0.43          0.55   0.02                                             c       0.10          0.55   0.35                                             d       0.55          0.10   0.35                                             ______________________________________                                    

ZnAPSO compositions are generally synthesized by hydrothermalcrystallization at effective process conditions from a reaction mixturecontaining active sources of zinc, silicon, aluminum and phosphorus,preferably an organic templating, i.e., structure-directing, agent,preferably a compound of an element or Group VA of the Periodic Table,and/or optionally an alkali of other metal. The reaction mixture isgenerally placed in a sealed pressure vessel, preferably lined with aninert plastic material such as polytetrafluoroethylene and heated,preferably under autogenous pressure at a temperature between 50° C. and250° C., and preferably between 100° C. and 200° C. until crystals ofthe ZnAPSO product are obtained, usually a period of from several hoursto several weeks. Generally the effective crystallization period is fromabout 2 hours to about 30 days with typical periods of from about 4hours to about 20 days being employed to obtain ZnAPSO products. Theproduct is recovered by any convenient method such as centrifugation orfiltration.

In synthesizing the ZnAPSO compositions, it is preferred to employ areaction mixture composition expressed in terms of the molar ratios asfollows:

    aR: (Zn.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 : bH.sub.2 O

wherein "R" is an organic templating agent; "a" is the amount of organictemplating agent "R" and has a value of from zero to about 6 and ispreferably an effective amount within the range of greater than zero (0)to about 6; "b" has a value of from zero (0) to about 500, morepreferably between about 2 and about 300; and "w", "x", "y" and "z"represent the mole fractions of zinc, aluminum, phosphorus and silicon,respectively, and each has a value of at least 0.01. In a preferredembodiment the reaction mixture is selected such that the mole fractions"w", "x", "y" and "z" are generally defined as being within the limitingcompositional values or points as follows:

    ______________________________________                                        Mole Fraction                                                                 Point   x             y      (z + w)                                          ______________________________________                                        F       0.60          0.38   0.02                                             G       0.38          0.60   0.02                                             H       0.01          0.60   0.39                                             I       0.01          0.01   0.98                                             J       0.60          0.01   0.39                                             ______________________________________                                    

In the foregoing expression of the reaction composition, the reactantsare normalized with respect to the total of "w", "x", "y" and "z" suchthat (w+x+y+z)=1.00 mole. Molecular sieves containing zinc, aluminum,phosphorus and silicon as framework tetrahedral oxide units are preparedas follows:

Preparative Reagents

ZnAPSO compositions are typically prepared using numerous reagents.Reagents which may be employed to prepare ZnAPSOs include:

(a) Alipro: aluminum isopropoxide;

(b) LUDOX-LS: LUDOX LS is the trade name of DuPont for an aqueoussolution of 30 weight percent SiO₂ and 0.1 weight percent Na₂ ;

(c) CATAPAL: Trademark of Condea Corporation for hydratedpseudoboehmite;

(d) H₃ PO₄ : 85 weight percent aqueous phosphoric acid;

(e) ZnAc: Zinc Acetate, Zn(C₂ H₃ O₂)₂ ·4H₂ O;

(f) TEAOH: 40 weight percent aqueous solution of tetraethylammoniumhydroxide;

(g) TBAOH: 40 weight percent aqueous solution of tetrabutylammoniumhydroxide;

(h) TMAOH: Tetramethylammonium hydroxide pentahydrate, (CH₃)₄ NOH·5H₂ O;

(i) TPAOH: 40 weight percent aqueous solution of tetrapropylammoniumhydroxide, (C₃ H₇)₄ NOH;

(j) Pr₂ NH: di-n-propylamine, (C₃ H₇)₂ NH;

(k) Pr₃ N: Tri-n-propylamine, (C₃ H₇)₃ N;

(l) Quin: Quinuclidine, (C₇ H₁₃ N);

(m) C-hex: cyclohexylamine; and

(n) DEEA: diethylethanolamine, (C₂ H₅)₂ NC₂ H₅ OH.

Preparative Procedure

ZnAPSO compositions are typically prepared by forming reaction mixtureshaving a molar composition expressed as:

    eR:fZnO:gAl.sub.2 O.sub.3 :hP.sub.2 O.sub.5 :iSiO.sub.2 :jH.sub.2 O

wherein e, f, g, h, i and j represent the moles of template R, zinc(expressed as the oxide), Al₂ O₃, P₂ O₅ (H₃ PO₄ expressed as P₂ O₅),SiO₂ and H₂ O, respectively.

The reaction mixtures are generally prepared by forming a startingreaction mixture comprising the H₃ PO₄ and a portion of the water. Thismixture is stirred and the aluminum source added. The resulting mixtureis blended until a homogeneous mixture is observed. The LUDOX LS is thenadded to the resulting mixture and the new mixture blended until ahomogeneous mixture is observed. The zinc source (zinc acetate) isdissolved in the remaining water and combined with the first mixture.The combined mixture is blended until a homogenous mixture is observed.The organic templating agent is added to this mixture and blended forabout two to four minutes until a homogenous mixture is observed. Theresulting mixture (final reaction mixture) is placed in a lined(polytetrafluoroethylene) stainless steel pressure vessel and digestedat an effective temperature for an effective time. Digestions aretypically carried out at the autogenous pressure. The products areremoved from the reaction vessel and cooled.

FeAPSO MOLECULAR SIEVES

The FeAPSO of U.S. Ser. No. 600,173, filed Apr. 13, 1984 have molecularsieves having a three dimensional microporous crystal frameworkstructures of FeO₂ ⁻², (and/or FeO₂ ⁻), AlO₂ ⁻, PO₂ ⁺ and SiO₂tetrahedral oxide units and having a unit empirical formula, on ananhydrous basis, of:

    mR: (Fe.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2            (1)

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the moles of "R"present per mole of (Fe_(w) Al_(x) P_(y) Si_(z))O₂ and has a value offrom zero (0) to about 0.3; the maximum value of "m" in each casedepends upon the molecular dimensions of the templating agent and theavailable void volume of the pore system of the particular molecularsieve involved; and "w", "x", "y" and "z" represent the mole fractionsof iron, aluminum, phosphorus and silicon, respectively, present astetrahedral oxides, said mole fractions being such that they are withinthe limiting compositional values or points as follows:

    ______________________________________                                        Mole Fraction                                                                 Point   x             y      (z + w)                                          ______________________________________                                        A       0.60          0.38   0.02                                             B       0.38          0.60   0.02                                             C       0.01          0.60   0.39                                             D       0.01          0.01   0.98                                             E       0.60          0.01   0.39                                             ______________________________________                                    

The values of w, x, y and z may be as follows:

    ______________________________________                                        Mole Fraction                                                                 Point   x             y      (z + w)                                          ______________________________________                                        a       0.55          0.43   0.02                                             b       0.43          0.55   0.02                                             c       0.10          0.55   0.35                                             d       0.55          0.10   0.35                                             ______________________________________                                    

The FeAPSOs of the instant invention are generally synthesized byhydrothermal crystallization from a reaction mixture comprising reactivesources of iron, aluminum, phosphorus and silicon, and preferably one ormore organic templating agents. Optionally, alkali or other metal(s) maybe present in the reaction mixture and may act as templating agents. Thereaction mixture is generally placed in a pressure vessel, preferablylined with an inert plastic material, such as polytetrafluoroethylene,and heated, preferably under the autogenous pressure, at an effectivetemperature which is generally between about 50° C., and about 250° C.and preferably between about 100° C. and 200° C. until crystals of theFeAPSO product are obtained, usually a period of from several hours toseveral weeks. Molecular sieves containing iron, aluminum phosphorus andsilicon as framework tetrahedral oxide units are typically prepared asfollows:

Preparative Reagents

FeAPSO compositions may be prepared using numerous reagents. Reagentswhich may employed to prepare FeAPSOs include:

(a) Alipro: aluminum isopropoxide, Al(OCH(CH₃)₂)₃ ;

(b) LUDOX-LS: LUDOX-LS is the trademark of Du Pont for an aqueoussolution of 30 weight percent SiO₂ and 0.1 weight percent Na₂ O;

(c) CATAPAL: trademark for hydrated aluminum oxide containing about 75wt. percent Al₂ O₃ (pseudoboehmite phase) and about 25 wt. percentwater;

(d) Fe(Ac)₂ : Iron (II) acetate;

(e) FeSO₄. Iron (II) sulfate hexahydrate;

(f) H₃ PO₄ : 85 weight percent phosphoric acid in water;

(g) TEAOH: 40 weight percent aqueous solution of tetraethylammoniumhydroxide;

(h) TBAOH: 40 weight percent aqueous solution of tetrabutylammoniumhydroxide;

(i) Pr₂ NH: di-n-propylamine ((C₃ H₇)₂ NH);

(j) Pr₃ N: tri-n-propylamine ((C₃ H₇)₃ N);

(k) Quin: Quinuclidine (C₇ H₁₃ N);

(l) MQuin: Methyl Quinuclidine hydroxide (C₇ H₁₃ NCH₃ OH);

(m) TMAOH: tetramethylammonium hydroxide pentahydrate; and

(o) C-hex: cyclohexylamine.

(a) Reaction mixtures to prepare FeAPSOs are typically prepared bygrinding an aluminum isopropoxide in a blender followed by slowly addinga H₃ PO₄ solution with mixing. A solution/dispersion of iron acetate inwater is added and then a silica (e.g., LUDOX-LS) is added. The organictemplating agent is then added to this mixture, or in some casesone-half of this mixture, and the mixture blended to form a homogeneousmixture. For example, in one embodiment, the number of moles of eachcomponent in the reaction mixture is as follows:

    ______________________________________                                               Component                                                                             Moles                                                          ______________________________________                                               Al.sub.2 O.sub.3                                                                      0.9                                                                   P.sub.2 O.sub.5                                                                       0.9                                                                   SiO.sub.2                                                                             0.2**                                                                 FeO*    0.2                                                                   TEAOH   1.0                                                                   H.sub.2 O                                                                             50                                                             ______________________________________                                         *Iron (II) acetate reported as Iron (II) oxide.                               **SiO.sub.2 was 0.6 in examples 5C to 8C                                 

The reaction mixture is sealed in a stainless steel pressure vessellined with polytetrafluoroethylene and heated in an oven at atemperature, time and at the autogenous pressure. The solid reactionproduct is recovered by filtration, washed with water and dried at roomtemperature.

In another embodiment, reaction mixtures are prepared by grinding thealuminum isopropoxide in a blender followed by addition of asolution/dispersion of iron (II) acetate. H₃ PO₄ is added to thismixture and the resulting mixture blended to form a homogeneous mixture.A silica e.g., LUDOX-LS) is added to this mixture except that in someinstances the silica may be added with the H₃ PO₄. The resultingmixtures were blended until a homogeneous mixture is observed. Organictemplating agent is added to each mixture and the resulting mixturesplaced in a stainless steel pressure vessel lined withpolytetrafluoroethylene and heated, washed and the product recovered. Inthis embodiment the number of moles of each component in the reactionmixture is as follows:

    ______________________________________                                               Component                                                                             Moles                                                          ______________________________________                                               Al.sub.2 O.sub.3                                                                      0.9                                                                   P.sub.2 O.sub.5                                                                       0.9                                                                   SiO.sub.2                                                                             0.2                                                                   FeO*    0.2                                                                   Template                                                                              1.0                                                                   H.sub.2 O                                                                             50                                                             ______________________________________                                         *Iron (II) acetate reported as Iron (II) oxide.                          

CoMnAPSO MOLECULAR SIEVES

CoMnAPSO molecular sieves of U.S. Ser. No. 600,168, filed Apr. 13, 1984,(EPC Publication No. 0 158 350, published Oct. 16, 1985), may beexpressed by the empirical chemical formula (anhydrous) as follows:

    mR: (Co.sub.u Mn.sub.v Al.sub.x P.sub.y Si.sub.z)O.sub.2

where "u", "v", "x", "y" and "z" represent the mole. The CoMnAPSOmolecular sieves have an empirical chemical composition on an anhydrousbasis expressed by the formula:

    mR: (Co.sub.u Mn.sub.v Al.sub.x P.sub.y Si.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the molar amount of "R"present per mole of (Co_(u) Mn_(v) Al_(x) P_(y) Si_(z))O₂ from zero (0)to about 0.3; and "u", "v", "x", "y" and "z" represent the molefractions of cobalt, manganese, aluminum, phosphorus and silicon,respectively, present as tetrahedral oxides. The mole fractions "u","v", "x", "y", and "z" are generally defined as being within thelimiting compositional values or points as follows, wherein "w", thecombined mole fractions of manganese and cobalt, is the sum of "u" and"v":

    ______________________________________                                        Mole Fraction                                                                 Point   x             y      (z + w)                                          ______________________________________                                        A       0.60          0.37   0.03                                             B       0.37          0.60   0.03                                             C       0.01          0.60   0.39                                             D       0.01          0.01   0.98                                             E       0.60          0.01   0.39                                             ______________________________________                                    

Preferably the mole fractions u, v, x, y and z will fall within thelimiting compositional values or points as follows:

    ______________________________________                                        Mole Fraction                                                                 Point   x             y      (z + w)                                          ______________________________________                                        a       0.55          0.42   0.03                                             b       0.42          0.55   0.03                                             c       0.10          0.55   0.35                                             d       0.55          0.10   0.35                                             ______________________________________                                    

CoMnAPSO compositions are generally synthesized by hydrothermalcrystallization from a reaction mixture containing reactive sources ofcobalt, manganese, aluminum, phosphorus and silicon and preferably anorganic templating agent, i.e., structure-directing, agent. Thestructure-directing agents are preferably a compound of an element ofGroup VA of the Periodic Table, and may be an alkali or other metal. Thereaction mixture is generally placed in a sealed pressure vessel,preferably lined with an inert plastic material such aspolytetrafluoroethylene and heated, preferably under autogenous pressureand at typical effective temperatures between 50° C. and 250° C.,preferably between 100° C. and 200° C., until crystals of the CoMnAPSOproduct are obtained, usually over a period of from several hours toseveral weeks. Typical effective crystallization times are from about 2hours to 30 days with from about 4 hours to about 20 days beinggenerally employed to obtain CoMnAPSO products. The product is recoveredby any convenient method such as centrifugation or filtration.

In synthesizing the CoMnAPSO compositions, it is preferred to employ areaction mixture composition expressed in terms of the molar ratios asfollows:

    aR: (Co.sub.u Mn.sub.v Al.sub.x P.sub.y Si.sub.z)O.sub.2 : bH.sub.2 O

wherein "R" is an organic templating agent; "a" is the amount of organictemplating agent "R" and has a value of from zero to about 6 and ispreferably an effective amount within the range of greater than zero (0)to about 6; "b" has a value of from zero (0) to about 500, preferablybetween about 2 and about 300; and "u", "v", "x", "y", and "z" representthe mole fractions of elements cobalt, manganese, aluminum, phosphorusand silicon, respectively, and each has a value of at least 0.01.

In one embodiment the reaction mixture is selected such that the molefractions "w", "x", "y" and "z" are generally defined as being withinthe limiting compositional values or points as follows:

    ______________________________________                                        Mole Fraction                                                                 Point   x             y      (z + w)                                          ______________________________________                                        F       0.60          0.37   0.03                                             G       0.37          0.60   0.03                                             H       0.01          0.60   0.39                                             I       0.01          0.01   0.98                                             J       0.60          0.01   0.39                                             ______________________________________                                    

In the foregoing expression of the reaction composition, the reactantsare normalized with respect to the total of "u", "v", "x", "y" and "z"such that (u+v+x+y+z)=1.00 mole. CoMnAPSO compositions were preparedusing numerous regents.

Reagents which may be employed to prepare CoMnAPSOs include:

(a) Alipro: aluminum isopropoxide;

(b) LUDOX-LS: LUDOX-LS is the tradename of DuPont for an aqueoussolution of 30 weight percent SiO₂ and 0.1 weight percent Na₂ O;

(c) H₃ PO₄ : 85 weight percent phosphoric acid;

(d) MnAc: Manganese acetate, Mn(C₂ H₃ O₂)₂ ·4H₂ O;

(e) CoAc: Cobalt Acetate, Co(C₂ H₃ O₂)₂ ·4H₂ O;

(f) TEAOH: 40 weight percent aqueous solution of tetraethylammoniumhydroxide; and

(g) Pr₂ NH: di-n-propylamine, (C₃ H₇)₂ NH.

Preparative Procedures

CoMnAPSOs may be prepared by forming a starting reaction mixture byadding H₃ PO₄ and one half of the quantity of water. To this mixture analuminum isopropoxide is added. This mixture is then blended until ahomogeneous mixture is observed. To this mixture a silica (e.g.,LUDOX-LS) is added and the resulting mixture blended (about 2 minutes)until a homogeneous mixture is observed. A second mixture is preparedusing manganese acetate and one half of the remaining water. A thirdmixture is prepared using cobalt acetate and one half of the remainingwater. The three mixtures are admixed and the resulting mixture blendeduntil a homogeneous mixture is observed. The organic templating agent isthen added to the resulting mixture and the resulting mixture blendeduntil a homogeneous mixture is observed, i.e., about 2 to 4 minutes. ThepH of the mixture is measured and adjusted for temperature. The mixtureis then placed in a lined (polytetrafluoroethylene) stainless steelpressure vessel and digested at a temperature. Digestions are typicallycarried out at the autogenous pressure.

CoMnMgAPSO MOLECULAR SIEVES

The CoMnMgAPSO molecular sieves of U.S. Ser. No. 600,182, filed April13, 1984 have three-dimensional microporous framework structures of CoO₂⁻², MnO₂ ⁻², MgO₂ ⁻², AlO₂ ⁻, PO₂ ⁺ and SiO₂ tetrahedral oxide units andhave an empirical chemical composition on an anhydrous basis expressedby the formula:

    mR: (Co.sub.t Mn.sub.u Mg.sub.v Al.sub.x P.sub.y Si.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the molar amount of "R"present per mole of (Co_(t) Mn_(u) Mg_(v) Al_(x) P_(y) Si_(z))O₂, andhas a value of from zero to about 0.3; and "t", "u", "v", "x", "y" and"z" represent the mole fractions of cobalt, manganese, magnesium,aluminum, phosphorus and silicon, respectively, present as tetrahedraloxides, each having a value of at least 0.01. The mole fractions "t","u", "v", "x", "y" and "z" are generally defined as being within thelimiting compositional values or points as follows, wherein "w", thecombined mole fractions of cobalt, manganese and magnesium, is the sumof "t", "u" and "v":

    ______________________________________                                        Mole Fraction                                                                 Point   x             y      (z + w)                                          ______________________________________                                        A       0.60          0.36   0.04                                             B       0.36          0.60   0.04                                             C       0.01          0.60   0.39                                             D       0.01          0.01   0.98                                             E       0.60          0.01   0.39                                             ______________________________________                                    

In a preferred subclass of the CoMnMgAPSO molecular sieves the values of"w", "x", "y" and "z" in the above formula are within the limitingcompositional values or points as follows:

    ______________________________________                                        Mole Fraction                                                                 Point   x             y      (z + w)                                          ______________________________________                                        a       0.55          0.41   0.04                                             b       0.41          0.55   0.04                                             c       0.10          0.55   0.35                                             d       0.55          0.10   0.35                                             ______________________________________                                    

CoMnMgAPSO compositions are generally synthesized by hydrothermalcrystallization from a reaction mixture containing reactive sources ofcobalt, manganese, magnesium, aluminum, phosphorus and silicon, andpreferably an organic templating agent, i.e., structure-directing,agent. The structure-directing agents are preferably a compound of anelement of Group VA of the Periodic Table, and/or optionally an alkalior other metal. The reaction mixture is generally placed in a sealedpressure vessel, preferably lined with an inert plastic material such aspolytetrafluoroethylene and heated, preferably under autogenous pressureat a temperature between 50° C. and 250° C., and preferably between 100°C. and 200° C. until crystals of the CoMnMgAPSO product are obtained,usually over a period of from several hours to several weeks. Typicalcrystallization times are from about 2 hours to about 30 days with fromabout 4 hours to about 20 days generally being employed to obtainCoMnMgAPSO products. The product is recovered by any convenient methodsuch as centrifugation or filtration.

In synthesizing the CoMnMgAPSO compositions, it is preferred to employ areaction mixture composition expressed in terms of the molar ratios asfollows:

    aR: (Co.sub.t Mn.sub.u Mg.sub.v Al.sub.x P.sub.y Si.sub.z)O.sub.2 : bH.sub.2 O

wherein "R" is an organic templating agent; "a" is the amount of organictemplating agent "R" and has a value of from zero to about 6 and ispreferably an effective amount within the range of greater than zero (0)to about 6 and more preferably from greater than zero to about 2; "b"has a value of from zero (0) to about 500, preferably between about 2and about 300; and "t", "u", "v", "x", "y", and "z" represent the molefractions of cobalt, manganese, magnesium, aluminum, phosphorus andsilicon, respectively, and each has a value of at least 0.01.

In a preferred embodiment the reaction mixture is selected such that themole fractions "w", "x", "y" and "z", where "w" is the sum of"t"+"u"+"v", are generally defined as being within the limitingcompositional values or points as follows:

    ______________________________________                                        Mole Fraction                                                                 Point   x             y      (z + w)                                          ______________________________________                                        F       0.60          0.36   0.04                                             G       0.36          0.60   0.04                                             H       0.01          0.60   0.39                                             I       0.01          0.01   0.98                                             J       0.60          0.01   0.39                                             ______________________________________                                    

In the foregoing expression of the reaction composition, the reactantsare normalized with respect to the total of "t", "u", "v", "x", "y" and"z" such that (t+u+v+x+y+z)=1.00 mole. Molecular sieves containingcobalt, manganese, magnesium, aluminum, phosphorus and silicon asframework tetrahedral oxide units are prepared as follows:

Preparative Reagents

CoMnMgAPSO compositions may be prepared by numerous reagents. Reagentswhich may be employed to prepare CoMnAPSOs include:

(a) Alipro: aluminum isopropoxide;

(b) LUDOX-LS: LUDOX-LS is the tradename of Du Pont for an aqueoussolution of 30 weight percent SiO₂ and 0.1 weight percent Na₂ O;

(c) H₃ PO₄ : aqueous solution which is 85 weight percent phosphoricacid;

(d) MnAc: Manganese acetate, Mn(C₂ H₃ O₂)₂ ·4H₂ O;

(e) CoAc: Cobalt Acetate, Co(C₂ H₃ O₂)₂ ·4H₂ O;

(f) MgAc: Magnesium Acetate Mg(C₂ H₃ O₂)·4H₂ O;

(g) TEAOH: 40 weight percent aqueous solution of tetraethylammoniumhydroxide; and

(h) Pr₂ NH: di-n-propylamine, (C₃ H₇)₂ NH.

Preparative Procedures

CoMnMgAPSOs may be prepared by forming a starting reaction mixture byadding H₃ PO₄ and one half of the quantity of water. To this mixture analuminum isopropoxide is added. This mixture is then blended until ahomogeneous mixture is observed. To this mixture a silica (e.g.,LUDOX-LS) is added and the resulting mixture blended (about 2 minutes)until a homogeneous mixture is observed.

Three additional mixtures are prepared using cobalt acetate, magnesiumacetate and manganese acetate using one third of the remainder of thewater for each mixture. The four mixtures are then admixed and theresulting mixture blended until a homogeneous mixture is observed. Anorganic templating agent is then added to the resulting mixture and theresulting mixture blended until a homogeneous mixture is observed, i.e.,about 2 to 4 minutes. The mixture is then placed in a lined(polytetrafluoroethylene) stainless steel pressure vessel and digestedat a temperature for a time. Digestions are typically carried out at theautogenous pressure.

MeAOP MOLECULAR SIEVES

MeAPO molecular sieves are crystalline microporous aluminophosphates inwhich the substituent metal is one of a mixture of two or more divalentmetals of the group magnesium, manganese, zinc and cobalt and aredisclosed in U.S. Pat. No. 4,567,029. Members of this novel class ofcompositions have a three-dimensional microporous crystal frameworkstructure of MO₂ ⁻², AlO₂ ⁻ and PO₂ ⁺ tetrahedral units and have anessential empirical chemical composition, on an anhydrous basis, of:

    mR:(M.sub.x Al.sub.y P.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the moles of "R"present per mole of (M_(x) Al_(y) P_(z))O₂ and has a value of from zeroto 0.3 maximum value in each case depending upon the moleculardimensions of the templating agent and the available void volume of thepore system of the particular metal aluminophosphate involved; "x", "y",and "z" represent the mole fractions of the metal "M", (i.e., magnesium,manganese, zinc and cobalt), aluminum and phosphorus, respectively,present as tetrahedral oxides, said mole fractions being such that theyare representing the following values for "x", "y", and "z":

    ______________________________________                                        Mole Fraction                                                                 Point   x              y      z                                               ______________________________________                                        A       0.01           0.60   0.39                                            B       0.01           0.39   0.60                                            C       0.35           0.05   0.60                                            D       0.35           0.60   0.05                                            ______________________________________                                    

When synthesized the minimum value of "m" in the formula above is 0.02.In a preferred subclass of the metal aluminophosphates of thisinvention, the values of "x", "y" and "z" in the formula above arerepresenting the following values for "x", "y" and "z":

    ______________________________________                                        Mole Fraction                                                                 Point   x              y      z                                               ______________________________________                                        a       0.01           0.52   0.47                                            b       0.01           0.39   0.60                                            c       0.25           0.15   0.60                                            d       0.25           0.40   0.35                                            ______________________________________                                    

The as-synthesized compositions are capable of withstanding 350° C.calcination in air for extended periods, i.e., at least 2 hours, withoutbecoming amorphous. While it is believed that the M, Al and P frameworkconstituents are present in tetrahedral coordination with oxygen, it istheoretically possible that some minor fraction of these frameworkconstituents are present in coordination with five or six oxygen atoms.It is not, moreover, necessarily the case that all of the M, Al and/or Pcontent of any given synthesized product be a part of the framework inthe aforesaid types of coordination with oxygen. Some of eachconstituent may be merely occluded or in some as yet undetermined formand may or may not be structurally significant.

Since the term "metal aluminophosphate" is somewhat cumbersome,particularly in view of the need for numerous repetitions thereof indescribing such compositions, the "short hand" reference "MeAPO" isemployed hereinafter. Also in those cases where the metal "Me" in thecomposition is magnesium, the acronym MAPO is applied to thecomposition. Similarly, ZAPO, MnAPO, and CoAPO are applied to thecompositions which contain zinc, manganese and cobalt, respectively. Toidentify the various structural species which make up each of thesubgeneric classes MAPO, ZAPO, CoAPO and MnAPO, each species is assigneda number and is identified, for example, as ZAPO-5, MAPO-11, CoAPO 11and so forth.

The term "essential empirical chemical composition" is meant to includethe crystal framework and can include any organic templating agentpresent in the pore system, but does not include alkali metal or otherions which can be present by virtue of being contained in the reactionmixture or as a result of post synthesis ion-exchange. Such ionicspecies, when present, function primarily as charge-balancing ions forAlO₂ ⁻ and/or MO₂ ⁻² tetrahedra not associated PO₂ ⁺ tetrahedra or anorganic ion derived with P02 from the organic templating agent.

The metal aluminophosphates ("MeAPOs" ) are synthesized by hydrothermalcrystallization from a reaction mixture containing reactive sources ofthe metal "M", alumina and phosphate, an organic templating, i.e.,structure-directing, agent, preferably a compound of an element of GroupVA of the Periodic Table, and optionally an alkali metal. The reactionmixture is placed in a sealed pressure vessel, preferably lined with aninert plastic material such as polytetrafluoroethylene and heated,preferably under autogenous pressure at a temperature between 100° C.and 225° C., and preferably between 100° C. and 200° C. until crystalsof the metal aluminophosphate product are obtained, usually a period offrom 4 hours to 2 weeks. The product is recovered by any convenientmethod such as centrifugation or filtration.

In synthesizing the MeAPO compositions, it is preferred to employ areaction mixture composition expressed in terms of molar ratios asfollows:

    aR:(M.sub.x Al.sub.y P.sub.z)O.sub.2 :bH.sub.2 O

wherein "R" is an organic templating agent; "a" has a value great enoughto constitute an effective concentration of "R" and is within the rangheof >0 to 6; "b" has a value of from zero to 500, preferably 2 to 30; "M"represents a metal of the roup zinc, magnesium, manganese and cobalt,"x", "y" and "z" represent the mole fractions, respectively, of "M",aluminum and phosphorus in the (M_(x) Al_(y) P_(z))O₂ constituent, andeach has a value of at least 0.01, the said points E, F, G, H, I, and Jrepresenting the following values for "x", "y" and "z":

    ______________________________________                                        Mole Fraction                                                                 Point   x              y      z                                               ______________________________________                                        E       0.01           0.70   0.29                                            F       0.01           0.29   0.70                                            G       0.29           0.01   0.70                                            H       0.40           0.01   0.59                                            I       0.40           0.59   0.01                                            J       0.29           0.70   0.01                                            ______________________________________                                    

In the foregoing expression of the reaction composition, the reactantsare normalized with respect to a total of (M+Al+P)=(x+y+z)=1.00 mole.

In forming the reaction mixture from which the metal aluminophosphatesare crystallized the organic templating agent can be any of thoseheretofore proposed for use in the synthesis of conventional zeolitealuminosilicates and microporous aluminophosphates. In general thesecompounds contain elements of Group VA of the Periodic Table ofElements, particularly nitrogen, phosphorus, arsenic and antimony,preferably N or P and most preferably N, which compounds also contain atleast one alkyl or aryl group having from 1 to 8 carbon atoms.Particularly preferred nitrogen-containing compounds for use astemplating agents are the amines and quaternary ammonium compounds, thelatter being represented generally by the formula R₄ N⁺ wherein each Ris an alkyl or aryl group containing from 1 to 8 carbon atoms. Polymericquaternary ammonium salts such as [(C₁₄ H₃₂ N₂) (OH)₂ ]_(x) wherein "x"has a value of at least 2 are also suitably employed. Both mono- , di-and triamines are advantageously utilized, either alone or incombination with a quaternary ammonium compound or other templatingcompound. Mixtures of two or more templating agents can either producemixtures of the desired metal aluminophosphates or the more stronglydirecting templating species may control the course of the reaction withthe other templating species serving primarily to establish the pHconditions of the reaction gel. Representative templating agents includetetramethylammonium, tetraethylammonium, tetrapropylammonium ortetrabutylammonium ions; di-n-propylamine; tripropylamine;triethylamine; triethanolamine; piperidine; cyclohexylamine;2-methylpyridine; N,N-dimethylbenzylamine; N-N-dimethylethanolamine;choline; N,N'-dimethylpiperazine; 1,4-diazabicyclo (2,2,2) octane;N-methyldiethanolamine, N-methylethanolamine; N-methylpiperidine;3-methylpiperidine; N-methylcyclohexylamine; 3-methylpyridine;4-methylpyridine; quinuclidine; N,N'-dimethyl-1,4 -diazabicyclo (2,2,2)octane ion; di-n-butylamine, neopentylamine; di-n-pentylamine;isopropylamine; t-butylamine; ethylenediamine; pyrrolidine; and2-imidazolidone. Not every templating agent will direct the formation ofevery species of metal aluminophosphate (MeAPO), i.e., a singletemplating agent can, with proper manipulation of the reactionconditions, direct the formation of several MeAPO compositions, and agiven MeAPO composition can be produced using several differenttemplating agents.

The preferred phosphorus source is phosphoric acid, but organicphosphates such as triethylphosphate have been found satisfactory, andso also have crystalline or amorphous aluminophosphates such as theAlPO₄ composition of U.S. Pat. No. 4,310,440. Organo-phosphoruscompounds, such as tetrabutylphosphonium bromide do not, apparentlyserve as reactive sources of phosphorus, but these compounds do functionas templating agents. Conventional phosphorus salts such as sodiummetaphosphate, may be used, at least in part, as the phosphorus source,but are not preferred.

The aluminum source is preferably either an aluminum alkoxide, such asaluminum isoproproxide, or pseudoboehmite. The crystalline or amorphousaluminophosphates which are a suitable source of phosphorus are, ofcourse, also suitable sources of aluminum. Other sources of aluminumused in zeolite synthesis, such as gibbsite, sodium aluminate andaluminum trichloride, can be employed but are not preferred.

The metals zinc, cobalt, magnesium and manganese can be introduced intothe reaction system in any form which permits the formation in situ ofreactive divalent ions of the respective metals. Advantageously salts,oxides or hydroxides of the metals are employed such as cobalt chloridehexahydrate, alpha cobaltous iodide, cobaltous sulfate, cobalt acetate,cobaltous bromide, cobaltous chloride, zinc acetate, zinc bromide, zincformate, zinc iodide, zinc sulfate heptahydrate, magnesium acetate,magnesium bromide, magnesium chloride, magnesium iodide, magnesiumnitrate, magnesium sulfate, manganous acetate, manganous bromide,manganous sulfate, and the like.

While not essential to the synthesis of MeAPO compositions, it has beenfound that in general, stirring or other moderate agitation of thereaction mixture and/or seeding the reaction mixture with seed crystalsof either the MeAPO species to be produced or a topologically similaraluminophosphate or aluminosilicate composition, facilitates thecrystallization procedure.

After crystallization the MeAPO product is isolated and advantageouslywashed with water and dried in air. The as-synthesized MeAPO containswithin its internal pore system at least one form of the templatingagent employed in its formation. Most commonly the organic moiety ispresent, at least in part, as a charge-balancing cation as is generallythe case with as-synthesized aluminosilicate zeolites prepared fromorganic-containing reaction systems. It is possible, however, that someor all of the organic moiety is an occluded molecular species in aparticular MeAPO species. As a general rule, the templating agent, andhence the occluded organic species, is too large to move freely throughthe pore system of the MeAPO product and must be removed by calciningthe MeAPO at temperatures of 200° C. to 700° C. to thermally degrade theorganic species. In a few instances the pores of the MeAPO product aresufficiently large to permit transport of the templating agent,particularly if the latter is a small molecule, and accordingly completeor partial removal thereof can be accomplished by conventionaldesorption procedures such as carried out in the case of zeolites. Itwill be understood that the term "as-synthesized" as used herein and inthe claims does not include the condition of the MeAPO phase wherein theorganic moiety occupying the intracrystalline pore system as a result ofthe hydrothermal crystallization process has been reduced by postsynthesis treatment such that the value of "m" in the compositionformula:

    mR:(M.sub.x Al.sub.y P.sub.z)O.sub.2

has a value of less than 0.02. The other symbols of the formula are asdefined hereinabove. In those preparations in which an aluminum alkoxideis employed as the source of aluminum, the corresponding alcohol isnecessarily present in the reaction mixture since it is a hydrolysisproduct of the alkoxide. It has not been determined whether this alcoholparticipates in the syntheses process as a templating agent. For thepurposes of this application, however, this alcohol is arbitrarilyomitted from the class of templating agents, even if it is present inthe as-synthesized MeAPO material.

Since the MeAPO compositions are formed from AlO₂, PO₂, and MO₂tetrahedral units which, respectively, have a net charge of -1, +1, and-2, the matter of cation exchangeability is considerably morecomplicated than in the case of zeolitic molecular sieves in which,ideally, there is a stoichiometric relationship between AlO₂ tetrahedraand charge-balancing cations. In the MeAPO compositions, an AlO₂ ⁻tetrahedron can be balanced electrically either by association with aPO₂ ⁺ tetrahedron or a simple cation such as an alkali metal cation, acation of the metal "M" present in the reaction mixture, or an organiccation derived from the templating agent. Similarly an MO₂ ⁻²tetrahedron can be balanced electrically by association with PO₂ ⁺tetrahedra, a cation of the metal "M", organic cations derived from thetemplating agent, or other divalent or polyvalent metal cationsintroduced from an extraneous source. It has also been postulated thatnon-adjacent AlO₂ ⁻ and PO₂ ⁺ tetrahedral pairs can be balanced by Na⁺and OH⁻, respectively [Flanigen and Grose, Molecular Sieve Zeolites-I,ACS, Washington, D.C. (1971)].

FAPO MOLECULAR SIEVES

Ferroaluminophosphates are disclosed in U.S. Pat. No. 4,554,143,incorporated herein by reference, and have a three-dimensionalmicroporous crystal framework structure of AlO₂, FeO₂, and PO₂tetrahedral units and have an essential empirical chemical composition,on an anhydrous basis, of:

    mR:(Fe.sub.x Al.sub.y P.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the moles of "R"present per mole of (Fe_(x) Al_(y) P_(z))O₂ and has a value of from zeroto 0.3 maximum value in each case depending upon the moleculardimensions of the templating agent and the available void volume of thepore system of the particular ferroaluminophosphate involved; "x", "y",and "z" represent the mole fractions of iron, aluminum and phosphorus,respectively, present as tetrahedral oxides, representing the followingvalues for "x", "y", and "z":

    ______________________________________                                        Mole Fraction                                                                 Point   x              y      z                                               ______________________________________                                        A       0.01           0.60   0.39                                            B       0.01           0.39   0.60                                            C       0.35           0.05   0.60                                            D       0.35           0.60   0.05                                            ______________________________________                                    

When synthesized the minimum value of "m" in the formula above is 0.02.In a preferred subclass of the ferroaluminophosphates the values of "x","y" and "z" in the formula above are representing the following valuesfor "x", "y" and "z":

    ______________________________________                                        Mole Fraction                                                                 Point   x              y      z                                               ______________________________________                                        a       0.01           0.52   0.47                                            b       0.01           0.39   0.60                                            c       0.25           0.15   0.60                                            d       0.25           0.40   0.35                                            ______________________________________                                    

The iron of the FeO₂ structural units can be in either the ferric orferrous valence state, depending largely upon the source of the iron inthe synthesis gel. Thus, an FeO₂ tetrahedron in the structure can have anet charge of either -1 or -2. While it is believed that the Fe, Al andP framework constituents are present in tetrahedral coordination withoxygen (and are referred to herein as such), it is theoreticallypossible that some minor fraction of these framework constituents arepresent in coordination with five or six oxygen atoms. It is not,moreover, necessarily the case that all of the Fe, Al and/or P contentof any given synthesized product is a part of the framework in theaforesaid types of coordination with oxygen. Some of each constituentmay be merely occluded or in some as yet undetermined form, and may ormay not be structurally significant.

For convenience in describing the ferroaluminophosphates, the "shorthand" acronym "FAPO" is sometimes employed hereinafter. To identify thevarious structural species which make up the generic class FAPO, eachspecies is assigned a number and is identified, for example, as FAPO-11,FAPO-31 and so forth.

The term "essential empirical chemical composition" is meant to includethe crystal framework and can include any organic templating agentpresent in the pore system, but does not include alkali metal or otherions which can be present by virtue of being contained in the reactionmixture or as a result of post-synthesis ion-exchange. Such ionicspecies, when present, function primarily as charge-balancing ions forFeO₂ ⁻ and/or AlO₂ ⁻² tetrahedra, FeO₂ ⁻² tetrahedra associated with PO₂⁺ tetrahedra or not associated with PO₂ ⁺ tetrahedra or an organic ionderived from the organic templating agent.

The aforesaid ferroaluminophosphates are synthesized by hydrothermalcrystallization from a reaction mixture containing reactive sources ofiron oxide, alumina and phosphate, an organic templating, i.e.,structure-directing, agent, preferably a compound of an element of GroupVA of the Periodic Table, and optionally an alkali metal. The reactionmixture is placed in a sealed pressure vessel, preferably lined with aninert plastic material such as polytetrafluoroethylene and heated,preferably under autogenous pressure at a temperature of at least 100°C., and preferably between 100° C. and 250° C. until crystals of themetal aluminophosphate product are obtained, usually a period of from 2hours to 2 weeks. The product is recovered by any convenient method suchas centrifugation or filtration.

In synthesizing the FAPO compositions, it is preferred to employ areaction mixture composition expressed in terms of molar ratios asfollows:

    aR:(Fe.sub.x Al.sub.y P.sub.z)O.sub.2 :bH.sub.2 O

wherein "R" is an organic templating agent; "a" has a value great enoughto constitute an effective concentration of "R" and is within the rangeof >0 to 6; "b" has a value of from zero to 500, preferably 2 to 80;"x", "y" and "z" represent the mole fractions, respectively, of iron,aluminum and phosphorus in the (Fe_(x) Al_(y) P_(z))O₂ constituent, andeach has a value of at least 0.01, and representing the following valuesfor "x", "y" and "z":

    ______________________________________                                        Mole Fraction                                                                 Point   x              y      z                                               ______________________________________                                        E       0.01           0.70   0.29                                            F       0.01           0.29   0.70                                            G       0.29           0.01   0.70                                            H       0.40           0.01   0.59                                            I       0.40           0.59   0.01                                            J       0.29           0.70   0.01                                            ______________________________________                                    

In the foregoing expression of the reaction composition, the reactantsare normalized with respect to a total of (Fe+Al+P)=(x+y+z)=1.00 mole.

In forming the reaction mixture from which the ferroaluminophosphatesare crystallized, the organic templating agent can be any of thoseheretofore proposed for use in the synthesis of conventional zeolitealuminosilicates and microporous aluminophosphates. In general thesecompounds contain elements of Group VA of the Periodic Table ofElements, particularly nitrogen, phosphorus, arsenic and antimony,preferably N or P and most preferably N, which compounds also contain atleast one alkyl or aryl group having from 1 to 8 carbon atoms.Particularly preferred nitrogen-containing compounds for use astemplating agents are the amines and quaternary ammonium compounds, thelatter being represented generally by the formula R₄ N⁺ wherein each Ris an alkyl or aryl group containing from 1 to 8 carbon atoms. Polymericquaternary ammonium salts such as [(C₁₄ H₃₂ N₂) (OH)₂ ]_(x) wherein "x"has a value of at least 2 are also suitably employed. Both mono-, di-and triamines are advantageously utilized, either alone or incombination with a quaternary ammonium compound or other templatingcompound. Mixtures of two or more templating agents can either producemixtures of the desired metal aluminophosphates or the more stronglydirecting templating species may control the course of the reaction withthe other templating species serving primarily to establish the pHconditions of the reaction gel. Representative templating agents includetetramethylammonium, tetraethylammonium, tetrapropylammonium ortetrabutylammonium ions; di-n-propylamine; tri-n-propylamine;triethylamine; triethanolamine; piperidine; cyclohexylamine;2-methylpyridine; N,N-dimethylbenzylamine; N-N-dimethylethanolamine;choline; N,N'-dimethylpiperazine; 1,4-diazabicyclo (2,2,2) octane;N-methyldiethanolamine, N-methylethanolamine; N-methylpiperidine;3-methylpiperidine; N-methylcyclohexylamine; 3-methylpyridine;4-methylpyridine; quinuclidine; N,N'-dimethyl-1,4-diazabicyclo (2,2,2)octane ion; di-n-butylamine, neopentylamine; di-n-pentylamine;isopropylamine; t-butylamine; ethylenediamine; pyrrolidine; and2-imidazolidone. Not every templating agent will direct the formation ofevery species of ferroaluminophosphate (FAPO), i.e., a single templatingagent can, with proper manipulation of the reaction conditions, directthe formation of several FAPO compositions, and a given FAPO compositioncan be produced using several different templating agents.

The phosphorus source is preferably phosphoric acid, but organicphosphates such as triethylphosphate have been found satisfactory, andso also have crystalline or amorphous aluminophosphates such as theAlPO₄ composition of U.S. Pat. No. 4,310,440. Organo-phosphoruscompounds, such as tetrabutylphosphonium bromide do not, apparentlyserve as reactive sources of phosphorus, but these compounds do functionas templating agents. Conventional phosphorus salts such as sodiummetaphosphate, may be used, at least in part, as the phosphorus source,but are not preferred.

The aluminum source is preferably either an aluminum alkoxide, such asaluminum isoproproxide, or pseudoboehmite. The crystalline or amorphousaluminophosphates which are a suitable source of phosphorus are, ofcourse, also suitable sources of aluminum. Other sources of aluminumused in zeolite synthesis, such as gibbsite, sodium aluminate andaluminum trichloride, can be employed but are not preferred.

Iron can be introduced into the reaction system in any form whichpermits the formation in situ of reactive ferrous or ferric ions.Advantageously iron salts, oxides or hydroxides are employed such asiron sulfate, iron acetate, iron nitrate, or the like. Other sourcessuch as a freshly precipitated iron oxide γ-FeOOH, are also suitable.

While not essential to the synthesis of FAPO compositions, it has beenfound that in general, stirring or other moderate agitation of thereaction mixture and/or seeding the reaction mixture with seed crystalsof either the FAPO species to be produced or a topologically similaraluminophosphate or aluminosilicate composition, facilitates thecrystallization procedure.

After crystallization the FAPO product is isolated and advantageouslywashed with water and dried in air. The as-synthesized FAPO containswithin its internal pore system at least one form of the templatingagent employed in its formation. Most commonly the organic moiety ispresent, at least in part, as a charge-balancing cation as is generallythe case with as-synthesized aluminosilicate zeolites prepared fromorganic-containing reaction systems. It is possible, however, that someor all of the organic moiety is an occluded molecular species in aparticular FAPO species. As a general rule, the templating agent, andhence the occluded organic species, is too large to move freely throughthe pore system of the FAPO product and must be removed by calcining theFAPO at temperatures of 200° C. to 700° C. to thermally degrade theorganic species. In a few instances the pores of the FAPO product aresufficiently large to permit transport of the templating agent,particularly if the latter is a small molecule, and accordingly completeor partial removal thereof can be accomplished by conventionaldesorption procedures such as carried out in the case of zeolites. Itwill be understood that the term "as-synthesized" as used herein and inthe claims does not include the condition of the FAPO phase wherein theorganic moiety occupying the intracrystalline pore system as a result ofthe hydrothermal crystallization process has been reduced bypost-synthesis treatment such that the value of "m" in the compositionformula:

    mR:(Fe.sub.x Al.sub.y P.sub.z)O.sub.2

has a value of less than 0.02. The other symbols of the formula are asdefined hereinabove. In those preparations in which an aluminum alkoxideis employed as the source of aluminum, the corresponding alcohol isnecessarily present in the reaction mixture since it is a hydrolysisproduct of the alkoxide. It has not been determined whether this alcoholparticipates in the syntheses process as a templating agent. For thepurposes of this application, however, this alcohol is arbitrarilyomitted from the class of templating agents, even if it is present inthe as-synthesized FAPO material.

Since the FAPO compositions are formed from AlO₂ ⁻, PO₂ ⁺, FeO₂ ⁻ and/orFeO₂ ⁻² units the matter of cation exchangeability is considerably morecomplicated than in the case of zeolitic molecular sieves in which,ideally, there is a stoichiometric relationship between AlO₂ tetrahedraand charge-balancing cations. In the FAPO compositions, an AIO₂ ⁻tetrahedron can be balanced electrically either by association with aPO₂ ⁺ tetrahedron or a simple cation such as an alkali metal cation, aFe⁺² or Fe⁺³ cation present in the reaction mixture, or an organiccation derived from the templating agent. Similarly an FeO₂ ⁻ or FeO₂ ⁻²tetrahedron can be balanced electrically by association with PO₂ ⁺tetrahedron, a Fe⁺² or Fe⁺³ cation, organic cations derived from thetemplating agent, or other metal cation introduced from an extraneoussource. It has also been postulated that non adjacent AlO₂ ⁻ and PO₂ ⁺tetrahedral pairs can be balanced by Na⁺ and OH⁻, respectively [Flanigenand Grose, Molecular Sieve Zeolites-I, ACS, Washington, D.C. (1971)].

TAPO MOLECULAR SIEVES

TAPO molecular sieves are disclosed in U.S. Pat. No. 4,500,561,incorporated herein by reference, and comprise a three-dimensionalmicroporous crystal framework structure of [TiO₂ ], [AlO₂ ] and [PO₂ ]tetrahedral units which has a unit empirical formula on an anhydrousbasis of:

    mR:(Ti.sub.x Al.sub.y P.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the moles of "R"present per mole of (Ti_(x) Al_(y) P_(z))O₂ and has a value of betweenzero and about 5.0, the maximum value in each case depending upon themolecular dimensions of the templating agent and the available voidvolume of pore system of the particular titanium molecular sieve; "x","y" and "z" represent the mole fractions of titanium, aluminum andphosphorus, respectively, present as tetrahedral oxides, representingthe following values for "x", "y" and "z":

    ______________________________________                                               Mole Fraction                                                          Point    x             y      z                                               ______________________________________                                        A        0.001         0.45   0.549                                           B        0.88          0.01   0.11                                            C        0.98          0.01   0.01                                            D        0.29          0.70   0.01                                            E        0.001         0.70   0.299                                           ______________________________________                                    

The parameters "x", "y" and "z" are preferably within the followingvalues for "x", "y" and "z":

    ______________________________________                                        Mole Fraction                                                                 Point   x             y       z                                               ______________________________________                                        A       0.002         0.499   0.499                                           b       0.20          0.40    0.40                                            c       0.20          0.50    0.30                                            d       0.10          0.60    0.30                                            e       0.002         0.60    0.398                                           ______________________________________                                    

The titanium-containing molecular sieves are referred to hereinafter,solely for point of reference herein as "TAPO" molecular sieves, or as"TAPOs" if the reference is to the class as a whole. This designation issimply made for the sake of convenient reference herein and is not meantto designate a particular structure for any given TAPO molecular sieve.The members of the class of TAPOs employed hereinafter in the exampleswill be characterized simply by referring to such members as TAPO-5,TAPO-11, etc., i.e., a particular species will be referred to as TAPO-nwhere "n" is a number specific to a given class member as itspreparation is reported herein. This designation is an arbitrary one andis not intended to denote structural relationship to another material(s)which may also be characterized by a numbering system.

The term "unit empirical formula" is used herein according to its commonmeaning to designate the simplest formula which gives the relativenumber of moles of titanium, aluminum and phosphorus which form the[TiO₂ ], [PO₂ ] and [AlO₂ ] tetrahedral unit within atitanium-containing molecular sieve and which forms the molecularframework of the TAPO composition(s). The unit empirical formula isgiven in terms of titanium, aluminum and phosphorus as shown in Formula(1), above, and does not include other compounds, cations or anionswhich may be present as a result of the preparation or the existence ofother impurities or materials in the bulk composition not containing theaforementioned tetrahedral unit. The amount of template R is reported aspart of the composition when the as-synthesized unit empirical formulais given, and water may also be reported unless such is defined as theanhydrous form. For convenience, coefficient "m" for template "R" isreported as a value that is normalized by dividing the number of molesof organic by the total moles of titanium, aluminum and phosphorus.

The unit empirical formula for a TAPO may be given on an"as-synthesized" basis or may be given after an "as-synthesized" TAPOcomposition has been subjected to some post treatment process, e.g.,calcination. The term "as-synthesized" herein shall be used to refer tothe TAPO composition(s) formed as a result of the hydrothermalcrystallization but before the TAPO composition has been subjected topost-treatment to remove any volatile components present therein. Theactual value of "m" for a post treated TAPO will depend on severalfactors (including: the particular TAPO, template, severity of thepost-treatment in terms of its ability to remove the template from theTAPO, the proposed application of the TAPO composition, etc.) and thevalue for "m" can be within the range of values as defined for theas-synthesized TAPO compositions although such is generally less thanthe as-synthesized TAPO unless such post-treatment process adds templateto the TAPO so treated. A TAPO composition which is in the calcined orother post-treatment form generally has an empirical formula representedby Formula (1), except that the value of "m" is generally less thanabout 0.02. Under sufficiently severe post-treatment conditions, e.g.,roasting in air at high temperature for long periods (over 1 hr.), thevalue of "m" may be zero (0) or, in any event, the template, R, isundetectable by normal analytical procedures.

The TAPO molecular sieves are generally further characterized by anintracrystalline adsorption capacity for water at 4.6 torr and about 24°C. of about 3.0 weight percent. The adsorption of water has beenobserved to be completely reversible while retaining the same essentialframework topology in both the hydrated and dehydrated state. The term"essential framework topology" is meant to designate the spatialarrangement of the primary bond linkages. A lack of change in theframework topology indicates that there is no disruption of theseprimary bond linkages.

The TAPO molecular sieves are generally synthesized by hydrothermalcrystallization from a reaction mixture comprising reactive sources oftitanium, aluminum and phosphorus, and one or more organic templatingagents. Optionally, alkali metal(s) may be present in the reactionmixture. The reaction mixture is placed in a pressure vessel, preferablylined with an inert plastic material, such as polytetrafluoroethylene,and heated, preferably under the autogenous pressure, at a temperatureof at least about 100° C., and preferably between 100° C. and 250° C.,until crystals of the molecular sieve product are obtained, usually fora period of from 2 hours to 2 weeks. While not essential to thesynthesis of the TAPO molecular sieves, it has been found that ingeneral stirring or other moderate agitation of the reaction mixtureand/or seeding the reaction mixture with seed crystals of either theTAPO to be produced, or a topologically similar composition, facilitatesthe crystallization procedure. The product is recovered by anyconvenient method such as centrifugation or filtration.

After crystallization the TAPO(s) may be isolated and washed with waterand dried in air. As a result of the hydrothermal crystallization, theas-synthesized TAPO contains within its intracrystalline pore system atleast one form of the template employed in its formation. Generally, thetemplate is a molecular species, but it is possible, stericconsiderations permitting, that at least some of the template is presentas a charge-balancing cation. Generally the template is too large tomove freely through the intracrystalline pore system of the formed TAPOand may be removed by a post-treatment process, such as by calcining theTAPO at temperatures of between about 200° C. and to about 700° C. so asto thermally degrade the template or by employing some otherpost-treatment process for removal of at least part of the template fromthe TAPO. In some instances the pores of the TAPO are sufficiently largeto permit transport of the template, and, accordingly, complete orpartial removal thereof can be accomplished by conventional desorptionprocedures such as carried out in the case of zeolites.

The TAPOs are preferably formed from a reaction mixture having a molefraction of alkali metal cation which is sufficiently low that it doesnot interfere with the formation of the TAPO composition. The TAPOcompositions are generally formed from a reaction mixture containingreactive sources of TiO₂, Al₂ O₃, and P₂ O₅ and an organic templatingagent, said reaction mixture comprising a composition expressed in termsof molar oxide ratios of:

    fR.sub.2 O:(Ti.sub.x Al.sub.y P.sub.z)O.sub.2 :g H.sub.2 O

wherein "R" is an organic templating agent; "f" has a value large enoughto constitute an effective amount of "R" said effective amount beingthat amount which form said TAPO compositions; "g" has a value of fromzero to 500; "x", "y" and "z" represent the mole fractions, respectivelyof titanium, aluminum and phosphorus in the (Ti_(x) Al_(y) P_(z))O₂constituent, and each has a value of at least 0.001 and being within thefollowing values for "x", "y" and "z":

    ______________________________________                                        Mole Fraction                                                                 Point   x             y       z                                               ______________________________________                                        h       0.001          0.989  0.01                                            i       0.001         0.01     0.989                                          j       0.32          0.24    0.44                                            k       0.98          0.01    0.01                                            ______________________________________                                    

Although the TAPO compositions will form if higher concentrations ofalkali metal cation are present, such reaction mixtures are notgenerally preferred. A reaction mixture, expressed in terms of molaroxide ratios, comprising the following bulk composition is preferred:

    oR.sub.2 O:wM.sub.2 O:(Ti.sub.x Al.sub.y P.sub.z)O.sub.2 :nH.sub.2 O

wherein "R" is an organic template; "o" has a value great enough toconstitute an effective concentration of "R" and is preferably withinthe range of from greater than zero (0) to about 5.0; "M" is an alkalimetal cation; "w" has a value of from zero to 2.5; "n" has a valuebetween about zero (0) and about 500; "x", "y" and "z" represent themole fractions, respectively, of titanium, aluminum and phosphorus in(Ti_(x) Al_(y) P_(z))O₂ "x", "y" and "z" represent the mole fractions,respectively of titanium, aluminum and phosphorus in the (Ti_(x) Al_(y)P_(z))O₂ constituent, and each has a value of at least 0.001 and beingwithin the following values for "x", "y" and "z":

    ______________________________________                                        Mole Fraction                                                                 Point   x             y       z                                               ______________________________________                                        h       0.001          0.989  0.01                                            i       0.001         0.01     0.989                                          j       0.32          0.24    0.44                                            k       0.98          0.01    0.01                                            ______________________________________                                    

When the TAPOs are synthesized by this method the value of "m" inFormula (1) is generally above about 0.02.

Though the presence of alkali metal cations is not preferred, when theyare present in the reaction mixture it is preferred to first admix atleast a portion (e.g., at least about 10 weight percent) of each of thealuminum and phosphorus sources in the substantial absence (e.g.,preferably less than about 20 percent of the total weight of thealuminum source and phosphorus source) of the titanium source. Thisprocedure avoids adding the phosphorus source to a basic reactionmixture containing the titanium source and aluminum source, (as was donein most of the published attempts to substitute isomorphously [PO₂ ]tetrahedra for [SiO₂ ] tetrahedra in zeolitic structures). Although thereaction mechanism is by no means clear at this time, the function ofthe template may be to favor the incorporation of [PO₂ ] and [AlO₂ ]tetrahedra in the framework structures of the crystalline products with[TiO₂ ] tetrahedra isomorphously replacing [PO₂ ] tetrahedra.

The reaction mixture from which these TAPOs are formed contains one ormore organic templating agents (templates) which can be most any ofthose heretofore proposed for use in the synthesis of aluminosilicatesand aluminophosphates. The template preferably contains at least oneelement of Group VA of the Periodic Table, particularly nitrogen,phosphorus, arsenic and/or antimony, more preferably nitrogen orphosphorus and most preferably nitrogen and are of the formula R₄ X⁺wherein X is selected from the group consisting of nitrogen, phosphorus,arsenic and/or antimony and R may be hydrogen, alkyl, aryl, aralkyl, oralkylaryl group and is preferably aryl or alkyl containing between 1 and8 carbon atoms, although more than eight carbon atoms may be present in"R" of group of the template. Nitrogen-containing templates arepreferred, including amines and quaternary ammonium compounds, thelatter being represented generally by the formula R'₄ N⁺ wherein each R'is an alkyl, aryl, alkylaryl, or araalkyl group; wherein R' preferablycontains from 1 to 8 carbon atoms or higher when R' is alkyl and greaterthan 6 carbon atoms when R' is otherwise, as hereinbefore discussed.Polymeric quaternary ammonium salts such as [(C₁₄ H₃₂ N₂) (OH)₂ ]_(x)wherein "x" has a value of at least 2 may also be employed. The mono-,di- and triamines, including mixed amines, may also be employed astemplates either alone or in combination with a quaternary ammoniumcompound or another template. The exact relationship of varioustemplates when concurrently employed is not clearly understood. Mixturesof two or more templating agents can produce either mixtures of TAPOs orin the instance where one template is more strongly directing thananother template the more strongly directing template may control thecourse of the hydrothermal crystallization wherein with the othertemplate serving primarily to establish the pH conditions of thereaction mixture.

Representative templates include tetramethylammonium,tetraethylammonium, tetrapropylammonium or tetrabutylammonium ions;di-n-propylamine; tripropylamine; triethylamine; triethanolamine;piperidine; cyclohexylamine; 2-methylpyridine; N,N-dimethylbenzylamine;N,N-diethylethanolamine; dicyclohexylamine; N,N-dimethylethanolamine;1,4-diazabicyclo (2,2,2) octane; N-methyldiethanolamine,N-methylethanolamine; N-methylcyclohexylamine; 3-methyl pyridine;4-methylpyridine; quinuclidine; N,N' -dimethyl-1,4-diazabicyclo (2,2,2)octane ion; di-n-butylamine, neopentylamine; di-n-pentylamine;isopropylamine; t-butylamine; ethylenediamine; pyrrolidine; and2-imidazolidone. As will be readily apparent from the illustrativeexamples set forth hereinafter, not every template will produce everyTAPO composition although a single template can, with proper selectionof the reaction conditions, cause the formation of different TAPOcompositions, and a given TAPO composition can be produced usingdifferent templates.

In those instances where an aluminum alkoxide is the reactive aluminumsource, the corresponding alcohol is necessarily present in the reactionmixture since it is a hydrolysis product of the alkoxide. It has not asyet been determined whether this alcohol participates in the synthesisprocess as a templating agent, or in some other function and,accordingly, is not reported as a template in the unit formula of theTAPOs, although such may be acting as templates.

Alkali metal cations, if present in the reaction mixture, may facilitatethe crystallization of certain TAPO phases, although the exact functionof such cations, when present, in crystallization, if any, is notpresently known. Alkali cations present in the reaction mixturegenerally appear in the formed TAPO composition, either as occluded(extraneous) cations and/or as structural cations balancing net negativecharges at various sites in the crystal lattice. It should be understoodthat although the unit formula for the TAPOs does not specificallyrecite the presence of alkali cations they are not excluded in the samesense that hydrogen cations and/or hydroxyl groups are not specificallyprovided for in the traditional formulae for zeolitic aluminosilicates.

Most any reactive titanium source may be employed herein. The preferredreactive titanium sources include titanium alkoxides, water-solubletitanates and titanium chelates.

Most any reactive phosphorous source may be employed. Phosphoric acid isthe most suitable phosphorus source employed to date. Accordingly, otheracids of phosphorus are generally believed to be suitable phosphorussources for use herein. Organic phosphates such as triethyl phosphatehave been found satisfactory, and so also have crystalline or amorphousaluminophosphates such as the AlPO₄ compositions of U.S. Pat. No.4,310,440. Organo-phosphorus compounds, such as tetrabutyl-phosphoniumbromide have not, apparently, served as reactive sources of phosphorus,but these compounds do function as templating agents and may also becapable of being suitable phosphorus sources under proper processconditions (yet to be ascertained). Organic phosphorus compounds, e.g.,esters, are believed to be generally suitable since they can generateacids of phosphorus in situ. Conventional phosphorus salts, such assodium metaphosphate, may be used, at least in part as the phosphorussource, but they are not preferred.

Most any reactive aluminum source may be employed herein. The preferredreactive aluminum sources include aluminum alkoxides, such as aluminumisopropoxide, and pseudoboehmite. Crystalline or amorphousaluminophosphates which are a suitable source of phosphorus are, ofcourse, also suitable sources of aluminum. Other sources of aluminumused in zeolite synthesis, such as gibbsite, sodium aluminate andaluminum trichloride, can be employed but as generally not preferred.

Since the exact nature of the TAPO molecular sieves are not clearlyunderstood at present, although all are believed to contain [TiO₂ ]tetrahedra in the three-dimensional microporous crystal frameworkstructure, it is advantageous to characterize the TAPO molecular sievesby means of their chemical composition. This is due to the low level oftitanium present in certain of the TAPO molecular sieves prepared todate which makes it difficult to ascertain the exact nature of theinteraction between titanium, aluminum and phosphorus. As a result,although it is believed that titanium, [TiO₂ ], has substitutedisomorphously for [AlO₂ ] or [PO₂ ] tetrahedra, it is appropriate tocharacterize certain TAPO compositions by reference to their chemicalcomposition in terms of the mole ratios of oxides in the as-synthesizedand anhydrous form as:

    vR:pTiO.sub.2 :gAl.sub.2 O.sub.3 :rP.sub.2 O.sub.5

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "v" represents an effective amount ofthe organic templating agent to form said TAPO compositions andpreferably has a value between and including zero and about 3.0; "p","q" and "r" represent moles, respectively, of titanium, alumina andphosphorus pentaoxide, based on said moles being such that they arewithin the following values for "p", "q" and "r":

    ______________________________________                                        Mole Fraction                                                                 Point   p              q     r                                                ______________________________________                                        A       0.004          1.0   1.22                                             B       176            1.0   11.0                                             C       196            1.0   1.0                                              D       0.828          1.0   0.0143                                           E       0.003          1.0   0.427                                            ______________________________________                                    

The parameters "p", "q" and "r" are preferably within the followingvalues for "p", "q" and "r":

    ______________________________________                                        Mole Fraction                                                                 Point   p              q     r                                                ______________________________________                                        a       0.008          1.0   1.0                                              b       1.0            1.0   1.0                                              c       0.80           1.0   0.60                                             d       0.333          1.0   0.50                                             e       0.067          1.0   0.663                                            ______________________________________                                    

ELAPO MOLECULAR SIEVES

"ELAPO" molecular sieves are a class of crystalline molecular sieves inwhich at least one element capable of forming a three-dimensionalmicroporous framework form crystal framework structures of AlO₂ ⁻, PO₂ ⁺and MO₂ ^(n) tetrahedral oxide units wherein "MO₂ ^(n) " represents atleast one different element (other than Al or P) present as tetrahedraloxide units "MO₂ ^(n) " with charge "n" where "n" may be -3, -2, -1, 0or 30 1. The members of this novel class of molecular sieve compositionshave crystal framework structures of AlO₂ ⁻, PO₂ ⁺ and MO₂ ^(n)tetrahedral units and have an empirical chemical composition on ananhydrous basis expressed by the formula:

    mR:(M.sub.x Al.sub.y P.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the molar amount of "R"present per mole of (M_(x) Al_(y) P_(z))O₂ ; "M" represents at least oneelement capable of forming framework tetrahedral oxides; and "x", "y"and "z" represent the mole fractions of "M", aluminum and phosphorus,respectively, present as tetrahedral oxides. "M" is at least onedifferent elements (M₁) such that the molecular sieves contain at leastone framework tetrahedral units in addition to AlO₂ ⁻ and PO₂ ⁺. "M" isat least one element selected from the group consisting of arsenic,beryllium, boron, chromium, gallium, germanium and lithium, and when "M"denotes two elements the second element may be one of the aforementionedand/or is at least one element selected from the group consisting ofcobalt, iron, magnesium, manganese, titanium and zinc. ELAPOs and theirpreparation are disclosed in European patent application Ser. No.85104386.9, filed Apr. 11, 1985 (EPC Publication No. 0158976, publishedOctober 13, 1985, incorporated herein by reference) and 85104388.5,filed Apr. 11, 1985 (EPC Publication No. 158349, published Oct. 16,1985, incorporated herein by reference).

The ELAPO molecular sieves are generally referred to herein by theacronym or "ELAPO" to AlO₂ ⁻, PO₂ ⁺ and MO₂ ^(n) tetrahedral oxideunits. Actual class members will be identified by replacing the "EL" ofthe acronym with the elements present as MO₂ ^(N) tetrahedral units. Forexample, "MgBeAPO" designates a molecular sieve comprised of AlO₂ ⁻, PO₂⁺, MgO₂ ⁻² and BeO₂ ⁻² tetrahedral units. To identify various structuralspecies which make up each of the subgeneric classes, each species isassigned a number and is identified as "ELAPO-i" wherein "i" is aninteger. The given species designation is not intended to denote asimilarity in structure to any other species denominated by a similaridentification system.

The ELAPO molecular sieves comprise at least one additional elementcapable of forming framework tetrahedral oxide units (MO₂ ^(n)) to formcrystal framework structures with AlO₂ ⁻ and Po₂ ⁺ tetrahedral oxideunits wherein "M" represents at least one element capable of formingtetrahedral units "MO₂ ^(n) ", where "n" is -3, -2, -1, 0 or +1 and isat least one element selected from the group consisting of arsenic,beryllium, boron, chromium, gallium, germanium and lithium. When "M"denotes two elements "M" may also be at least one element selected fromthe group consisting of cobalt, iron, magnesium, manganese, titanium andzinc. For example, in each instance "M" includes at least one of thefirst group of elements, e.g., As, Be, etc., and when two or moreelements are present, the second and further elements may be selectedfrom the first group of elements and/or the second group of elements, asabove discussed.

The ELAPO molecular sieves have crystalline three-dimensionalmicroporous framework structures of AlO₂ ⁻, PO₂ ⁺ and MO₂ ^(n)tetrahedral units and have an empirical chemical composition on ananhydrous basis expressed by the formula:

    mR:(M.sub.x Al.sub.y P.sub.z)O.sub.2 ;

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the molar amount of "R"present per mole of (M_(x) Al_(y) P_(z))O₂ and has a value of zero toabout 0.3; "M" represents at least one element capable of formingframework tetrahedral oxides where "M" is at least one element selectedfrom the group consisting of arsenic, beryllium, boron, chrcmium,gallium, germanium and lithium. When "M" includes an additional elementsuch additional elements "M" may be at least one element selected fromthe group consisting of cobalt, iron, magnesium, manganese, titanium,and zinc.

The relative amounts of element(s) "M", aluminum and phosphorus areexpressed by the empirical chemical formula (anhydrous):

    mR:(M.sub.x Al.sub.y P.sub.z)O.sub.2

where "x", "y" and "z" represent the mole fractions of said "M",aluminum and phosphorus. The individual mole fractions of each "M" (orwhen M denotes two or more elements, M₁, M₂, M₃, etc.) may berepresented by "x₁ ", "x₂ ", "x₃ ", etc. wherein "x₁ ", "x₂ ", and "x₃", and etc. represent the individual mole fractions of elements M₁, M₂,M₃, etc. for "M" as above defined. The values of "x₁ ", "x₂ ", "x₃ ",etc. are as defined for "x", hereinafter, where "x₁ "+"x₂ "+"x₃ " . . .="x" and where x₁, x₂, x₃, etc. are each at least 0.01.

The ELAPO molecular sieves have crystalline three dimensionalmicroporous framework structures of MO₂ ^(n), AlO₂ ⁻ and PO₂ ⁺ unitshaving an empirical chemical composition on an anhydrous basis expressedby the formula:

    mR:(M.sub.x Al.sub.y P.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents a molar amount of "R"present per mole of (M_(x) Al_(y) P_(z))O₂ and has a value of zero toabout 0.3; "M" represents at least one different element (other than Alor P) capable of forming framework tetrahedral oxides, as hereinbeforedefined, and "x", "y" and "z" represent the mole fractions of "M",aluminum and phosphorus, respectively, present as tetrahedral oxides;said mole fractions "x", "y" and "z" being generally defined as withinthe following values for "x", "y", and "z":

    ______________________________________                                               Mole Fraction                                                          Point    x             y      z                                               ______________________________________                                        A        0.02          0.60   0.38                                            B        0.02          0.38   0.60                                            C        0.39          0.01   0.60                                            D        0.98          0.01   0.01                                            E        0.39          0.60   0.01                                            ______________________________________                                    

In a preferred sub class of the ELAPOs of this invention, the values of"x", "y" and "z" in the formula above are within the following valuesfor "x", "y" and "z":

    ______________________________________                                               Mole Fraction                                                          Point    x             y      z                                               ______________________________________                                        a        0.02          0.60   0.38                                            b        0.02          0.38   0.60                                            c        0.39          0.01   0.60                                            d        0.60          0.01   0.39                                            e        0.60          0.39   0.01                                            f        0.39          0.60   0.01                                            ______________________________________                                    

ELAPO compositions are generally synthesized by hydrothermalcrystallization from a reaction mixture containing reactive sources ofthe elements "M", aluminum and phosphorus, preferably an organictemplating, i.e., structure directing, agent, preferably a compound ofan element of Group VA of the Periodic Table, and/or optionally analkali or other metal. The reaction mixture is generally placed in asealed pressure vessel, preferably lined with an inert plastic materialsuch as polytetrafluoroethylene and heated, preferably under autogenouspressure at a temperature between 50° C. and 250° C., and preferablybetween 100° C. and 200° C. until crystals of the ELAPO product areobtained, usually a period of from several hours to several weeks.Typical crystallization times are from about 2 hours to about 30 dayswith from about 2 hours to about 20 days being generally employed toobtain crystals of the ELAPO products. The product is recovered by anyconvenient method such as centrifugation or filtration.

In synthesizing the ELAPO compositions of the instant invention, it ispreferred to employ a reaction mixture composition expressed in terms ofthe molar ratios as follows:

    aR:(M.sub.x Al.sub.y P.sub.z)O.sub.2 :bH.sub.2 O

wherein "R" is an organic templating agent; "a" is the amount of organictemplating agent "R" and has a value of from zero to about 6 and ispreferably an effective amount within the range of greater than zero (0)to about 6; "b" has a value of from zero (0) to about 500, preferablybetween about 2 and 300; "M" represents at least one element, as abovedescribed, capable of forming tetrahedral oxide framework units, MO₂^(n), with AlO₂ ⁻ and PO₂ ⁺ tetrahedral units; "n" has a value of -3,-2, -1, 0 or +1; and "x", "y" and "z" represent the mole fractions of"M", aluminum and phosphorus, respectively, "y" and "z" each have avalue of at least 0.01 and "x" has a value of at least 0.01 with eachelement "M" having a mole fraction of at least 0.01. The mole fractions"x", "y" and "z" are preferably within the following values for "x", "y"and "z":

    ______________________________________                                               Mole Fraction                                                          Point    x             y      z                                               ______________________________________                                        F        0.01          0.60   0.39                                            G        0.01          0.39   0.60                                            H        0.39          0.01   0.60                                            I        0.98          0.01   0.01                                            J        0 39          0.60   0.01                                            ______________________________________                                    

In the foregoing expression of the reaction composition, the reactantsare normalized with respect to a total of (M+Al+P)=(x+y+z)=1.00 mole,whereas in many of the working examples appearing hereinafter thereaction mixtures are expressed in terms of molar oxide ratios and maybe normalized to 1.00 mole of P₂ O₅. This latter form is readilyconverted to the former form by routine calculations by dividing thetotal number of moles of "M", aluminum and phosphorus into the moles ofeach of "M", aluminum and phosphorus. The moles of template and waterare similarly normalized by dividing the total moles of "M", aluminumand phosphorus.

In forming the reaction mixture from which the instant molecular sievesare formed the organic templating agent can be any of those heretoforeproposed for use in the synthesis of conventional zeolitealuminosilicates. In general these compounds contain elements of GroupVA of the Periodic Table of Elements, particularly nitrogen, phosphorus,arsenic and antimony, preferably nitrogen or phosphorus and mostpreferably nitrogen, which compounds also contain at least one alkyl oraryl group having from 1 to 8 carbon atoms. Particularly preferredcompounds for use as templating agents are the amines, quaternaryphosphonium compounds and quaternary ammonium compounds, the latter twobeing represented generally by the formula R₄ X⁺ nitrogen or phosphorusand each R is an alkyl or aryl group containing from 1 to 8 carbonatoms. Polymeric quaternary ammonium salts such as [(C₁₄ H₃₂ N₂) (OH)₂]_(x) wherein "x" has a value of at least 2 are also suitably employed.The mono-, di- and tri-amines are advantageously utilized, either aloneor in combination with a quaternary ammonium compound or othertemplating compound. Mixtures of two or more templating agents caneither produce mixtures of the desired ELAPOs or the more stronglydirecting templating species may control the course of the reaction withthe other templating species serving primarily to establish the pHconditions of the reaction gel. Representative templating agents includetetramethylammonium, tetraethylammonium, tetrapropylammonium ortetrabutylammonium ions; tetrapentylammonium ion; di-n propylamine;tripropylamine; triethylamine; triethanolamine; piperidine;cyclohexylamine; 2-methylpyridine; N,N dimethylbenzylamine; N,Ndimethylethanolamine; choline; N,N'-dimethylpiperazine; 1,4-diazabicyclo(2,2,2,) octane; N methyldiethanolamine, N-methylethanolamine;N-methylpiperidine; 3-methylpiperidine; N-methylcyclohexylamine;3-methylpyridine; 4-methylpyridine; quinuclidine;N,N'-dimethyl-1,4-diazabicyclo (2,2,2) octane ion; di-n butylamine,neopentylamine; di-n-pentylamine; isopropylamine; t-butylamine;ethylenediamine; pyrrolidine; and 2-imidazolidone. Not every templatingagent will direct the formation of every species of ELAPO, i.e., asingle templating agent can, with proper manipulation of the reactionconditions, direct the formation of several ELAPO compositions, and agiven ELAPO composition can be produced using several differenttemplating agents.

The phosphorus source is preferably phosphoric acid, but organicphosphates such as triethyl phosphate may be satisfactory, and so alsomay crystalline or amorphous aluminophosphates such as the AlPO₄composition of U.S. Pat. No. 4,310,440. Organo phosphorus compounds,such as tetrabutylphosphonium bromide, do not apparently serve asreactive sources of phosphorus, but these compounds may function astemplating agents. Conventional phosphorus salts such as sodiummetaphosphate, may be used, at least in part, as the phosphorus source,but are not preferred.

The aluminum source is preferably either an aluminum alkoxide, such asaluminum isoproproxide, or pseudoboehmite. The crystalline or amorphousaluminophosphates which are a suitable source of phosphorus are, ofcourse, also suitable sources of aluminum. Other sources of aluminumused in zeolite synthesis, such as gibbsite, sodium aluminate andaluminum trichloride, can be employed but are not preferred.

The element(s) "M" can be introduced into the reaction system in anyform which permits the formation in situ of reactive form of theelement, i.e., reactive to form the framework tetrahedral oxide unit ofthe element. The organic and inorganic salts, of "M" such as oxides,alkoxides, hydroxides, halides and carboxylates, may be employedincluding the chlorides, bromides, iodides, nitrates, sulfates,acetates, formates, ethoxides, propoxides and the like.

While not essential to the synthesis of ELAPO compositions, stirring orother moderate agitation of the reaction mixture and/or seeding thereaction mixture with seed crystals of either the ELAPO species to beproduced or a topologically similar species, such as aluminophosphate,aluminosilicate or molecular sieve compositions, facilitates thecrystallization procedure.

After crystallization the ELAPO product may be isolated andadvantageously washed with water and dried in air. The as-synthesizedELAPO generally contains within its internal pore system at least oneform of the templating agent employed in its formation. Most commonlythe organic moiety is present, at least in part, as a charge balancingcation as is generally the case with as-synthesized aluminosilicatezeolites prepared from organic containing reaction systems. It ispossible, however, that some or all of the organic moiety is an occludedmolecular species in a particular ELAPO species. As a general rule thetemplating agent, and hence the occluded organic species, is too largeto move freely through the pore system of the ELAPO product and must beremoved by calcining the ELAPO at temperatures of 200° C. to 700° C. tothermally degrade the organic species. In a few instances the pores ofthe ELAPO product are sufficiently large to permit transport of thetemplating agent, particularly if the latter is a small molecule, andaccordingly complete or partial removal thereof can be accomplished byconventional desorption procedures such as carried out in the case ofzeolites. It will be understood that the term "as synthesized" as usedherein does not include the condition of the ELAPO phase wherein theorganic moiety occupying the intracrystalline pore system as a result ofthe hydrothermal crystallization process has been reduced bypost-synthesis treatment such that the value of "m" in the compositionformula:

    mR:(M.sub.x Al.sub.y P.sub.z)O.sub.2

has a value of less than 0.02. The other symbols of the formula are asdefined hereinabove. In those preparations in which an alkoxide isemployed as the source of element "M", aluminum or phosphorus, thecorresponding alcohol is necessarily present in the reaction mixturesince it is a hydrolysis product of the alkoxide. It has not beendetermined whether this alcohol participates in the synthesis process asa templating agent. For the purposes of this application, however, thisalcohol is arbitrarily omitted from the class of templating agents, evenif it is present in the as-synthesized ELAPO material.

Since the present ELAPO compositions are formed from MO₂ ^(n), AlO₂, andPO₂ ⁺ tetrahedral oxide units which, respectively, have a net charge of"n", (where "m" may be -3, -2, -1, 0 or +1, -1 and +1, the matter ofcation exchangeability is considerably more complicated than in the caseof zeolitic molecular sieves in which, ideally, there is astoichiometric relationship between AlO₂ ⁻ tetrahedra andcharge-balancing cations. In the instant compositions, an AlO₂ ⁻tetrahedron can be balanced electrically either by association with aPO₂ ⁺ tetrahedron or a simple cation such as an alkali metal cation, aproton (H⁺), a cation of "M" present in the reaction mixture, or anorganic cation derived from the templating agent. Similarly an MO₂ ^(n)tetrahedron, where "n" is negative, can be balanced electrically byassociation with PO₂ ⁺ tetrahedra, a cation of "M" present in thereaction mixture, organic cations derived from the templating agent, asimple cation such as an alkali metal cation, or other divalent orpolyvalent metal cation, a proton (H⁺), anions or cations introducedfrom an extraneous source. It has also been postulated that non adjacentAlO₂ ⁻ and PO₂ ⁺ tetrahedral pairs can be balanced by Na⁺ and OH⁻respectively [Flanigen and Grose, Molecular Sieve Zeolites-I, ACS,Washington, DC (1971)]

DISCUSSION OF PROCESS

The term "light olefins" will be used hereinafter to refer to olefinshaving two to four carbon atoms, inclusive. Although other hydrocarbonproducts are formed, the products of particular interest herein are thelight olefins and they are preferably produced as the major hydrocarbonproducts, i.e., over 50 mole percent of the hydrocarbon product is lightolefins.

It has been discovered that the instant non-zeolitic molecular sievescan provide selectivity to C₂ to C₄ olefin products (i.e., ethylene,propylene, and butenes) of at least about 25 molar percent, based on thetotal hydrocarbon products formed, may be obtained, preferably in excessof 50 mole percent. Further, high molar conversions, i.e., preferably atleast about 70 percent and most preferably at least about 90 percent,based on the moles of feedstock to products, are believed obtainablewhile forming a minimum molar amount of methane (less than about ten(10) molar percent and preferably less than about five (5) molarpercent) and while forming only minor amounts of saturated hydrocarbonsand C₅ and higher hydrocarbons (typically less than about 10 molarpercent).

The instant process provides improved ethylene to propylene molar ratiosby carrying out the process in the presence of a diluent correlated tothe selected NZMS.

The instant process employs a feedstock comprising "aliphatic heterocompounds". The term "aliphatic hetero compounds" is employed herein toinclude alcohols, halides, mercaptans, sulfides, amines, ethers andcarbonyl compound (aldehydes, ketones, carboxylic acids, esters and thelike). The aliphatic moiety preferably contains from 1 to about 10carbon atoms and more preferably contains from 1 to about 4 carbonatoms. Suitable reactants include lower straight and branched (ofappropriate size) chain alkanols, their unsaturated counterparts, andthe nitrogen halogen and sulfur analogue of such. Representative ofsuitable aliphatic hetero compounds include: methanol; methyl chloride,methyl mercaptan; methyl sulfide; methyl amines; dimethyl ether;ethanol; ethyl mercaptan; ethyl chloride; diethyl ether; methylethylether; formaldehyde; dimethyl ketone; acetic acid; n-alkyl amines;n-alkyl halides and n-alkyl sulfides having n-alkyl group having 3 to 10carbon atoms; and mixtures thereof.

The instant process is preferably carried out in the vapor phase suchthat the feedstock is contacted in a vapor phase in a reaction zone witha non zeolitic molecular sieve at effective process conditions such asto produce light olefins, i.e., an effective temperature, pressure, WHSV(Weight Hourly Space Velocity) and with an effective amount of diluentto produce light olefins. Alternatively, the process may be carried outin a liquid phase. When the process is carried out in the liquid phasethe process necessarily involves the separation of products formed in aliquid reaction media and can result in different conversions andselectivities of feedstock to product with respect to the relativeratios of the liqht olefin products as compared to that formed by thevapor phase process.

The temperature which may be employed in the process may vary over awide range depending, at least in part, on the selected NZMS catalyst.In general, the process can be conducted at an effective temperaturebetween about 200° C. and about 700° C., preferably between about 250°C. and about 600° C., and most preferably between about 300° C. andabout 500° C. Temperatures outside the stated range are not excludedfrom the scope of this invention, although such do not fall withincertain desirable embodiments of the invention. At the lower end of thetemperature range and, thus, generally at the lower rate of reaction,the formation of the desired light olefin products may become markedlyslow. At the upper end of the temperature range and beyond, the processmay not form an optimum amount of light olefin products. Notwithstandingthese factors, the reaction will still occur and the feedstock, at leastin part, can be converted to the desired light olefin products attemperatures outside the range between about 200° C. and about 700 ° C.

The process is effectively carried out over a wide range of pressuresincluding autogenous pressures. At pressures between about 0.001atmospheres and about 1000 atmospheres, the formation of light olefinproducts will be effected although the optimum amount of product willnot necessarily form at all pressures. The preferred pressure is betweenabout 0.01 atmospheres and about 100 atmospheres. The pressures referredto herein for the process are exclusive of the diluent, and refer to thepartial pressure of the feedstock as it relates to the aliphatic heterocompounds and/or mixtures thereof. Pressures outside the stated rangeare not excluded from the scope of this invention, although such do notfall within certain desirable embodiments of the invention. At the lowerand upper end of the pressure range, and beyond, the selectivities,conversions and/or rates to light olefin products may not occur at theoptimum, although light olefin products can be formed.

The process is effected for a period of time sufficient to produce thedesired light olefin products. In general, the residence time employedto produce the desired product can vary from seconds to a number ofhours. It will be readily appreciated by one skilled in the art that theresidence time will be determined to a significant extent by thereaction temperature, the non zeolitic molecular sieve selected, theWHSV, the phase (liquid or vapor) selected, and, perhaps, selectedprocess design characteristics.

The process is effectively carried out over a wide range of WHSV for thefeedstock and is generally between about 0.01 hr⁻¹ 100 hr⁻¹ andpreferably between about 0.1 hr⁻¹ and about 40 hr⁻¹. Values above 100hr⁻¹ employed and are intended to be covered by the instant process,although such are not preferred.

The instant process is most preferably carried out under processconditions comprising a temperature between about 300° C. and about 500°C., a pressure between about 0.1 atmosphere (one atmosphere equals 14.7psia) to about 100 atmospheres, utilizing a WHSV expressed in hr⁻¹ foreach component of the feedstock having a value between about 0.1 andabout 40. The temperature, pressure, and WHSV are each selected suchthat the effective process conditions, i.e., the effective temperature,pressure, and WHSV, are employed in conjunction, i.e., correlated, withthe selected non zeolitic molecular sieve and selected feedstock suchthat light olefin products are produced.

The selection of the diluent is preferably such that the diluent iscorrelated to the selected NZMS such that the average kinetic diameterof the diluent molecules is greater than the average pore size of thenon-zeolitic molecular sieve. The selection of the diluent is alsorelated to the relative stability of the diluent under the processconditions. The average pore sizes of the NZMSs are such that thediluent is generally one or more cyclic compounds having 5 or more atomsin the ring, e.g., cycloalkanes, cycloalkenes, pyridine and aromaticcompounds. The diluent should be thermally stable under the processconditions. Aromatic compounds employable herein include compounds ofthe formula: ##STR1## wherein R₁, R₂, R₃, R₄, R₅, R₆ may be alkyl,alkylaryl, araalkyl, aryl and mixtures thereof, containing 1 to 20carbon atoms and optionally, hetero atoms (S, N, Cl, etc.). The diluentmay be selected from the group consisting of: cycloalkanes andsubstituted cycloalkanes (cyclopentane, cyclohexane); pyridine andsubstituted pyridine; benzene; alkyl benzenes including toluene,o-xylene, m-xylene, p-xylene, hemimellitene, pseudocumene, mesitylene,prehnitene, isodurene, durene, pentamethylbenzene, hexamethylbenzene,ethylbenzene, n-propylbenzene, cumene, n-butylbenzene, isobutylbenzene,sec-butylbenzene, tert-butylbenzene, p-cymene; biphenyl,diphenylmethane; triphenylmethane; 1,2-diphenylethane; anthracene;naphthalene; and the like.

In addition to the presence of the diluent that is correlated to theselected NZMS as above described, which may be present in an amountbetween about 1 and about 99 weight percent of the feedstock, and thealiphatic hetero compound(s) in the feedstock, other diluents may bepresent in the feedstock in place of such diluent in an amount betweenabout 1 and about 80 molar percent, based on the total number of molesof all feed and diluent components fed to the reaction zone (orcatalyst). Typical of additional diluents which may be employed in theinstant process are helium, argon, nitrogen, carbon monoxide, carbondioxide, hydrogen, water(steam), paraffins, hydrocarbons (such asmethane and the like), mixtures thereof, and the like.

It has been discovered that the addition of a diluent (correlated to thepore sizes of the selected NZMS), e.g., aromatic diluent, to a feedstockcomprising aliphatic hetero compounds is beneficial in increasing themolar ratio of ethylene to propylene in the hydrocarbon products. Inmany processes where ethylene is the desired light olefin this increasein the relative amount of ethylene may be of significant commercialimportance.

The instant process may be carried out in a batch, semi-continuous, orcontinuous fashion. The process can be conducted in a single reactionzone or a number of reaction zones arranged in series or in parallel, orit may be conducted intermittently or continuously in an elongatedtubular zone or a number of such zones. When multiple reaction zones areemployed, it may be advantageous to employ one or more of suchnon-zeolitic molecular sieves in series to provide for a desired productmixture. Owing to the nature of the process, it may be desirous to carryout the instant process by use of the NZMSs in a dynamic (e.g.,fluidized or moving) bed system or any system of a variety of transportbeds rather than in a fixed bed system. Such systems would readilyprovide for any regeneration (if required) of the non zeolitic molecularsieve catalyst after a given period of time. If regeneration isrequired, the non zeolitic molecular sieve catalyst can be continuouslyintroduced as a moving bed to a regeneration zone where it can beregenerated, such as for example by removing carbonaceous materials byoxidation in an oxygen-containing atmosphere. In the preferred practiceof the invention, the catalyst will be subject to a regeneration step byburning off carbonaceous deposits accumulated during reactions.

NON-ZEOLITIC MOLECULAR SIEVE CATALYSTS

The selection of the non-zeolitic molecular sieve catalysts for theinstant process is preferably related, in part, to the desired productmixture sought to be obtained. The selected non-zeolitic molecular sievedesirably has a kinetic pore diameter (average kinetic diameter inAngstroms, Å) such that the selectivity to the light olefin products isgreater than 50 molar percent. Accordingly, at least a portion,preferably a major portion, of the pores have an average kineticdiameter characterized such that the adsorption capacity (as measured bythe standard McBain-Bakr gravimetric adsorption method using givenadsorbate molecules) shows adsorption of oxygen (average kineticdiameter of about 3.46Å) and negligible adsorption of isobutane (averagekinetic diameter of about 5.0Å). More preferably the average kineticdiameter is characterized by adsorption of Xenon (average kineticdiameter of about 4.0Å) and negligible adsorption of isobutane and mostpreferably by adsorption of n-hexane (average kinetic diameter of about4.3Å) and negligible adsorption of isobutane. Negligible adsorption ofoxygen or xenon is adsorption of less than four percent by weight of theadsorbate based on the weight of the GZMS and adsorption of oxygen orxenon is adsorption of greater than or equal to four percent by weightof the adsorbate based on the weight of the NZMS. Negligible adsorptionof n-hexane or isobutane is adsorption of less than two percent byweight of the adsorbate based on the weight of the NZMS and adsorptionof n hexane or isobutane is adsorption of greater than or equal to twopercent by weight of the adsorbate based on the weight of the NZMS.Although it is clear that factors other than just the kinetic pore sizewill affect the products formed, including any occlusion of the pores,the exact nature of such other factors or their exact effect on theproducts formed are not understood at present. It is believed that thekinetic diameter of the pores of the non zeolitic molecular sieve isrelated to the products formed. Although a specific NZMS may not have akinetic pore diameter within the desired or preferred range the NZMS maybe modified by depositing or impregnating such with cations, anions,salts and/or compounds that occlude or otherwise result in themodification of a NZMS having a large pore size to one having a kineticpore diameter(s) within the desired or preferred range.

Techniques which may be employed to effect the diminution of the poresize of a non-zeolitic molecular sieve are generally known in the art.Such procedures generally involve the introduction to a pore of a poresize restricting material and may involve such procedures as (1)impregnating the NZMS with a solution comprising a solvent orsolubilizing agent for such a pore restricting material (one or more)inan amount sufficient to deposit the desired weight of such porerestricting material to the NZMS such that the desired pore size isobtained and/or (2) exchanging the NZMS with a solution containing thepore size restricting material. The impregnation or deposition of thepore restricting materials may be generally accomplished by heating theNZMS at an elevated temperature to evaporate any liquid present toeffect deposition or impregnation of the pore restricting material intothe interior and/or onto the exterior surface of the NZMS, or by theexchange of cations present in the NZMS with cations that provide forthe desired kinetic pore size. Alternatively, the pore restrictingmaterial may be formed on the NZMS from an emulsion or slurry containingthe pore restricting material by heating the NZMS as described above.Impregnation and exchange procedures are generally the preferredtechniques because they utilize and introduce the pore restrictingmaterial more efficiently than other procedures such as coatingprocedures since a coating procedure is generally not able to effectsubstantial introduction of the pore restricting material onto theinterior surfaces of the NZMS. In addition, coated materials are moregenerally susceptible to the loss of the pore restricting materials byabrasion.

Suitable pore restricting materials include alkali metal, alkaline earthmetals, transition metals and the salts thereof including inorganic andorganic salts such as: nitrates, halides, hydroxides, sulfates andcarboxylates. Other pore restricting materials generally employed in theart for such are also believed to be employable herein.

In carrying out the instant process the NZMS molecular sieves may beadmixed (blended) or provided sequential to other materials which mayprovide some property which is beneficial under process conditions, suchas improved temperature resistance or improved catalyst life byminimization of coking or which is simply inert under processconditions. Such materials may include synthetic or naturally occurringsubstances as well as inorganic materials such as clays, silicas,aluminas, crystalline aluminosilicate zeolites, metal oxides andmixtures thereof. In addition, the non zeolitic molecular sieves may beformed with materials such as silica, alumina, silica-alumina,silica-magnesia, silico-zirconia, silica-thoria, silica-berylia,silica-titania, as well as ternary compositions, such assilica-alumina-thoria, silica-alumina-zirconia and clays present asbinders. The relative proportions of the above materials and the NZMSmay vary widely with NZMS content ranging between about 1 and about 99percent by weight of the composite.

EXPERIMENTAL PROCEDURE (LIGHT OLEFIN PRODUCTION)

The production of light olefins in the examples was carried out bymixing about 0.5 gram of a selected NZMS with 2.5 grams of quartz chips(20-30 U.S. Standard mesh). The resulting mixture was then placed in a1/4 inch (outside diameter) No. 304 stainless steel tubular reactorhaving a wall thickness of 0.035 inch. The tubular reactor was immersedin a fluidized heated sand bath having electrical resistance heatersprovided for maintaining the sand bath and the tubular reactor at thedesired temperature. Thermocouples were provided for measurement of thereactor temperature.

A selected feedstock was introduced to the tubular reactor by means of aModel 100 Altex Metering Pump (from Altex Corporation, a subsidiary ofthe Beckmann Corporation) concurrently with a stream of diluent withnitrogen and water (steam) being employed as diluents (unless otherwisenoted in the examples hereinafter). The pressure employed in theexamples was the autogenous pressure about one (1) to about two (2)atmospheres unless otherwise noted. The ratios of feedstock componentsare reported as weight ratios. Nitrogen was employed as a diluent andwas introduced at a flow rate of about 5 cubic centimeters per minute.

The effluent from the tubular reactor (the reaction products) wasanalyzed. The liquid component of the effluent was collected at roomtemperature and subsequently analyzed by vapor phase chromatography,whereas the gaseous component of the effluent was sampled and analyzeddirectly from the effluent stream by vapor phase chromatography.

The analyses of both the liquid and vapor components of the effluentfrom the tubular reactor were carried out by programmed temperaturechromatography having a thermal conductivity detector with a programmedincrease in the chromatographic column's temperature over thechromatographic analysis. The analysis of the liquid and vaporouscomponents of the effluent, including the analysis of all standards wascarried out using chromatographic techniques by use of the followingchromatographic instruments:

    ______________________________________                                                   Phase Analyzed                                                                Liquid     Vapor                                                   ______________________________________                                        Chromatograph                                                                              Varian 3700  Hewlett Packard                                     Column       20 feet × 1/8                                                                        11 feet × 1/8                                              inch (O.D.)  inch (O.D.)                                                      stainless    stainless                                                        steel        steel                                               Packing      10% Carbowax Porapak R                                                        Chrom T 60/80                                                                 mesh                                                             ______________________________________                                    

Unless otherwise noted, the Molar Conversion to total products, based onmethanol ethanol, dimethyl ether, diethyl ether or mixtures thereof, was100% with the Molar Efficiency to a particular product being given as apercentage. When a product was not detected (ND) or if only a traceamount was qualitatively detected such is reported as ND or Trace (TR),respectively. The NZMSs employed in the following example aredenominated according to the nomenclature of the above mentionedapplications. The NZMSs of particular interest in the aforementionedapplications are those denominated therein by a "-n" designation where"n" is 17, 34, 35, 44 and 47. The NZMSs were calcined prior to their usein the examples. The following examples are provided to exemplify theinvention and are not meant to be limiting in any way.

PRODUCTION OF LIGHT OLEFINS: EXAMPLES Examples 1 to 9

NZMSs were employed as the catalyst for the conversion of methanol tolight olefins. The feedstock was a 70/30 by weight mixture of water tomethanol. In each case nitrogen was added at a flow rate of about 5cc/minute. The data in the Tables I to IX show that the NZMSs areeffective in converting methanol to light olefin products.

                  TABLE I                                                         ______________________________________                                        (MAPO-34).sup.1                                                                               Molar Selectivity, %                                                          375° C.                                                                        425° C.                                        ______________________________________                                        Ethylene          40.1      45.7                                              Ethane            1.5       0.9                                               Propylene         33.3      29.2                                              Propane           1.1       TR                                                Butenes           8.4       8.5                                               C.sub.5           1.2       1.6                                               C.sub.6           TR        TR                                                Methane           5.9       6.2                                               Carbon Dioxide    8.5       7.6                                               Dimethyl Ether    --        0.3                                               C.sub.2 -C.sub.4 Olefins                                                                        81.8      83.4                                              C.sub.2 /C.sub.3  1.20      1.57                                              WHSV (Methanol), hr.sup.-1                                                                      0.90      1.12                                              Run Time, hr      4.0       5.5                                               ______________________________________                                         .sup.1 MAPO34 is disclosed in U.S. Pat. No. 4,567,029.                   

                  TABLE II                                                        ______________________________________                                        (MAPO-35).sup.1                                                                               Molar Selectivity, %                                                          375° C.                                                                        425° C.                                        ______________________________________                                        Ethylene          52.1      47.7                                              Ethane            0.5       0.5                                               Propylene         27.3      26.8                                              Propane           ND        ND                                                Butenes           4.7       5.4                                               C.sub.5           3.1       1.7                                               C.sub.6           TR        TR                                                Methane           10.6      13.3                                              Carbon Dioxide    1.7       4.6                                               C.sub.2 -C.sub.4 Olefins                                                                        84.2      79.9                                              C.sub.2 /C.sub.3  1.91      1.78                                              Methanol Conversion, %                                                                          63.0      71.0                                              Dimethyl Ether Yield, %                                                                         26.9      7.6                                               WHSV (Methanol), hr.sup.-1                                                                      0.78      1.00                                              Run Time, hr      1.0       0.5                                               ______________________________________                                         .sup.1 MAPO35 is disclosed in U.S. Pat. No. 4,567,029.                   

                  TABLE III                                                       ______________________________________                                        (CoAPSO-34)                                                                                   Molar Selectivity, %                                                          375° C.                                                                        425° C.                                        ______________________________________                                        Ethylene          38.1      46.8                                              Ethane            0.8       0.5                                               Propylene         36.0      23.2                                              Propane           TR        ND                                                Butenes           9.2       5.4                                               C.sub.5           1.4       1.3                                               C.sub.6           0.1       0.4                                               Methane           3.8       8.3                                               Carbon Dioxide    10.6      13.9                                              Dimethyl Ether    TR        TR                                                C.sub.2 -C.sub.4 Olefins                                                                        83.4      75.4                                              C.sub.2 /C.sub.3  1.06      2.02                                              WHSV (Methanol), hr.sup.-1                                                                      0.95      0.93                                              Run Time, hr      2.5       4.8                                               ______________________________________                                    

                  TABLE IV                                                        ______________________________________                                        (CoAPO-34).sup.1                                                                              Molar Selectivity, %                                                          375° C.                                                                        425° C.                                        ______________________________________                                        Ethylene          37.7      45.3                                              Ethane            2.3       0.8                                               Propylene         38.6      27.1                                              Propane           TR        TR                                                Butenes           12.9      8.3                                               C.sub.5           3.2       1.4                                               C.sub.6           1.1       0.8                                               Methane           2.4       6.2                                               Carbon Dioxide    1.7       10.0                                              Dimethyl Ether    ND        ND                                                C.sub.2 -C.sub.4 Olefins                                                                        89.2      80.7                                              C.sub.2 /C.sub.3  0.98      1.67                                              WHSV (Methanol), hr.sup.-1                                                                      0.96      0.94                                              Run Time, hr      1.0       4.8                                               ______________________________________                                         .sup.1 CoAPO34 is disclosed in U.S. Pat. No. 4,567,029.                  

                  TABLE V                                                         ______________________________________                                        (TiAPSO-34)                                                                                   Molar Selectivity, %                                                          375° C.                                                                        425° C.                                        ______________________________________                                        Ethylene          44.6      53.5                                              Ethane            0.9       0.9                                               Propylene         40.4      29.1                                              Propane           ND        ND                                                Butenes           9.9       5.6                                               C.sub.5           1.6       0.7                                               C.sub.6           0.1       0.1                                               Methane           1.6       4.2                                               Carbon Dioxide    0.9       5.8                                               Dimethyl Ether    TR        TR                                                C.sub.2 -C.sub.4 Olefins                                                                        94.9      88.3                                              C.sub.2 /C.sub.3  1.10      1.84                                              WHSV (Methanol), hr.sup.-1                                                                      0.98      0.83                                              Run Time, hr      6.3       10.0                                              ______________________________________                                    

                  TABLE VI                                                        ______________________________________                                        (MgAPSO-34)                                                                                   Molar Selectivity, %                                                          375° C.                                                                        425° C.                                        ______________________________________                                        Ethylene          41.9      50.0                                              Ethane            0.6       0.6                                               Propylene         40.3      28.5                                              Propane           ND        ND                                                Butenes           11.7      7.4                                               C.sub.5           2.1       1.3                                               C.sub.6           0.2       0.1                                               Methane           1.8       5.6                                               Carbon Dioxide    1.3       6.5                                               Dimethyl Ether    TR        ND                                                C.sub.2 -C.sub.4 Olefins                                                                        93.9      86.0                                              C.sub.2 /C.sub.3  1.04      1.76                                              WHSV (Methanol), hr.sup.-1                                                                      0.92      0.91                                              Run Time, hr      4.0       7.0                                               ______________________________________                                    

                  TABLE VII                                                       ______________________________________                                        (MgAPSO-35)                                                                                  Molar Selectivity, %                                                          425° C.                                                 ______________________________________                                        Ethylene         44.1                                                         Ethane           2.6                                                          Propylene        21.0                                                         Propane          TR                                                           Butenes          5.7                                                          C.sub.5          2.5                                                          C.sub.6          0.7                                                          Methane          13.9                                                         Carbon Dioxide   9.4                                                          Dimethyl Ether   ND                                                           C.sub.2 -C.sub.4 Olefins                                                                       70.8                                                         C.sub.2 /C.sub.3 2.1                                                          WHSV (Methanol), hr.sup.-1                                                                     0.92                                                         Run Time, hr     1.0                                                          ______________________________________                                    

                  TABLE VIII                                                      ______________________________________                                        (MnAPO-34).sup.1                                                                             Molar Selectivity, %                                                          425° C.                                                 ______________________________________                                        Ethylene         43.6                                                         Ethane           0.6                                                          Propylene        31.1                                                         Propane          ND                                                           Butenes          10.4                                                         C.sub.5          1.7                                                          C.sub.6          0.2                                                          Methane          4.7                                                          Carbon Dioxide   7.6                                                          Dimethyl Ether   TR                                                           C.sub.2 -C.sub.4 Olefins                                                                       85.1                                                         C.sub.2 /C.sub.3 1.40                                                         WHSV (Methanol), hr.sup.-1                                                                     0.92                                                         Run Time, hr     3.3                                                          ______________________________________                                         .sup.1 MnAPO34 is disclosed in U.S. Pat. No. 4,567,029.                  

                  TABLE IX                                                        ______________________________________                                        (ZnAPSO-34)                                                                                   Molar Selectivity, %                                                          375° C.                                                                        425° C.                                        ______________________________________                                        Ethylene          40.6      51.3                                              Ethane            0.2       0.1                                               Propylene         41.3      30.6                                              Propane           ND        ND                                                Butenes           14.6      11.4                                              C.sub.5           1.6       0.9                                               C.sub.6           0.1       0.1                                               Methane           1.3       4.0                                               Carbon Dioxide    0.2       1.5                                               Dimethyl Ether    TR        TR                                                C.sub.2 -C.sub.4 Olefins                                                                        96.5      93.3                                              C.sub.2 /C.sub.3  0.98      1.67                                              WHSV (Methanol), hr.sup.-1                                                                      0.92      0.92                                              Run Time, hr      2.0       3.5                                               ______________________________________                                    

What is claimed is:
 1. A process for selectively making light olefinscontaining 2 to 4 carbon atoms which comprises contacting a feedstockcomprising aliphatic hetero compounds and mixtures thereof with anon-zeolitic molecular sieve NZMS, selected from the group consisting ofELAPSOs, CoAPSOs, FeAPSOs, MgAPSOs, MnAPSOs, TiAPSOs, ZnAPSOs,CoMnAPSOs, CoMngAPSOs, ELAPOs, MeAPOs, TAPOs, FAPOs and mixtures thereofat effective process conditions to selectively produce light olefins. 2.The process of claim 1 wherein said process is carried out in thepresence of a diluent.
 3. The process of claim 1 wherein the NZMS ischaracterized by adsorption of oxygen and negligible adsorption ofisobutane.
 4. The process of claim 1 wherein the NZMS is characterizedby adsorption of Xenon and negligible adsorption of isobutane.
 5. Theprocess of claim 1 wherein the NZMS is characterized by adsorption ofn-hexane and negligible adsorption of isobutane.
 6. The process of claim2 for making light olefins containing 2 to 4 carbon atoms whichcomprises contacting a feedstock comprising aliphatic hetero compoundsand mixtures thereof with a non-zeolitic molecular sieve in the presenceof an aromatic diluent.
 7. The process of claim 1 wherein said NZMS isselected from the group consisting of CoAPSOs, FeAPSOs, MgAPSOs,MnAPSOs, TiAPSOs, ZnAPSOs, CoMgAPSOs, CoMnMgAPSOs and mixtures thereof.8. The process of claim 1 wherein said NZMS is selected from the groupconsisting of NZMSs having an "-n" designation wherein "n" is selectedfrom the group consisting of 17, 34, 35, 44 and
 47. 9. The process ofclaim 1 wherein said NZMS is selected from the group consisting ofMAPO-34, MAPO-35, CoAPSO-34, CoAPO-34, MgAPSO 34, MgAPSO-35, MnAPSO-34,ZnAPSO-34 and mixtures thereof.
 10. The process of claim 1 wherein saidNZMS is selected from the group consisting of MeAPO-11, MeAPO-31,MeAPO-34, MeAPO-41, TAPO-11, TAPO-31, TAPO-34, TAPO-41, FAPO-11,FAPO-31, FAPO-41 and mixtures thereof.
 11. The process of claim 10wherein "Me" is selected from the group consisting of cobalt magnesium,manganese and mixtures thereof.
 12. The process of claim 10 wherein "Me"is selected from the group consisting of magnesium, manganese andmixtures thereof.
 13. The process of claim 1 wherein the aliphatichetero compound is selected from the group consisting of alcohols,ethers, amines, mercaptans, aldehydes, ketones, halides and mixturesthereof wherein the aliphatic moiety contains from 1 to about 10 carbonatoms.
 14. The process of claim 6 wherein light olefins constitute atleast about 25 molar percent the hydrocarbon products.
 15. The processof claim 14 wherein light olefin products constitute in excess of 5%molar percent of the hydrocarbon products.
 16. The process of claim 6wherein said diluent is selected from the group consisting ofcycloalkanes, pyridine and aromatic compounds of the formula: ##STR2##wherein R₁, R₂, R₃, R₄, R₅, and R₆ may be alkyl, araalkyl, aryl,alkylaryl or mixtures thereof containing from 1 to 20 carbon or heteroatoms.
 17. The process of claim 16 wherein said aromatic diluent isselected from the group consisting of benzene, toluene, o-xylene,m-xylene, p-xylene, hemimellitene, pseudocumene, mesitylene, prehnitene,isodurene, durene, pentamethylbenzene, hexmethylbenzene, ethylbenzene,n-propylbenzene, cumene, n-butylbenzene, isobutylbenzene,sec-butylbenzene, tert-butylbenzene, p-cymene, biphenyl,diphenylmethane, triphenyl methane, anthracene; naphthalene;1,2-diphenylethane and mixtures thereof.
 18. The process of claim 1 or 6wherein the feedstock is contacted with said NZMS at a temperaturebetween about 200° C. and about 700° C.
 19. The process of claim 18wherein the feedstock is contacted with said NZMS at a temperaturebetween about 250° C. and about 600° C.
 20. The process of claim 1 or 6wherein the process is conducted at a pressure between about 0.1atmosphere and about 1000 atmospheres.
 21. The process of claim 20wherein the process is conducted at a pressure between about 0.1atmosphere and about 100 atmospheres.
 22. The process of claim 1 or 6wherein said process is carried out in the vapor phase.
 23. The processof claim 1 or 6 wherein said process is carried out in the liquid phase.24. The process of claim 1 or 6 wherein the WHSV is between about 0.01hr⁻¹ and about 100 hr⁻¹.
 25. The process of claim 24 wherein the WHSV isbetween about 0.1 hr⁻¹ and about 40 hr⁻¹.
 26. The process of claim 1wherein the feedstock comprises methanol.
 27. The process of claim 1wherein the feedstock comprises methanol and dimethyl ether.
 28. Theprocess of claim 1 wherein the feedstock comprises ethanol.
 29. Theprocess of claim 1 wherein the feedstock comprises ethanol and diethylether.
 30. The process of claim 1 wherein the feedstock consistsessentially of methanol, dimethyl ether and an aromatic diluent selectedfrom the group consisting of benzene, toluene, xylene and mixturesthereof.
 31. The process of claim 1 wherein the feedstock comprises atleast one of methanol, ethanol and dimethyl ether and an aromaticdiluent selected from the group consisting of benzene, toluene, xyleneand mixtures thereof.
 32. The process of claim 1 wherein said feedstockcomprises of at least one of the methanol, ethanol, and dimethyl ether,from 1 weight percent to about 99 weight percent of an aromatic diluent,at a temperature between about 200° C. and about 700° C., at a pressurebetween about 0.01 atmospheres and about 1000 atmospheres, at a WHSVbetween about 0.01 hr⁻¹ and about 100 hr⁻¹.